KR20130114785A - Novel organic electroluminescent compounds and organic electroluminescent device containing the same - Google Patents

Abstract

PURPOSE: An organic electroluminescent compound has excellent luminous efficiency without using a hole-blocking layer and improves power efficiency. CONSTITUTION: An organic electroluminescent compound is represented by chemical formula 1-4. In the chemical formulas, each of X1 and X2 is CRO or N; at least one or more of X1 and X2 is N; each of Ar1, Ar2, and Ar3 is hydrogen, a substituted or unsubstituted C6-30 aryl group; or a substituted or unsubstituted 5-60 membered heteroaryl; each of L1, L2, and L3 is a single bond or a substituted or unsubstituted C6-30 arylene; each of A, B, C, and D ring is a substituted or unsubstituted C6-30 aromatic ring or a substituted or unsubstituted 5-60 membered aromatic hetero ring; and E has a structure represented by chemical formula 5.

Description

Novel organic electroluminescent compound and organic electroluminescent device including the same {NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE CONTAINING THE SAME}

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. More specifically, the present invention relates to a novel organic electroluminescent compound exhibiting excellent performance as a red luminescent material and an organic electroluminescent device comprising the same.

In the organic electroluminescent device, when a voltage is applied between the anode and the cathode, holes and electrons are injected into the anode and the cathode, respectively. These holes and electrons recombine in the light emitting layer to form an exciton. Emitting element using the principle of emitting light of a wavelength corresponding to the energy difference.

Such a luminescence is classified into a fluorescence using a singlet state exciton and a phosphorescence using a triplet state exciton according to the mechanism. For a quantum mechanical reason, a phosphorescent material can achieve luminous efficiency four times higher than that of a fluorescent material .

Meanwhile, in the organic electroluminescent device, a light emitting material (dopant) may be mixed with a host material to increase color purity, luminous efficiency and stability.

When the host material / dopant system is used as the light emitting material, the host material greatly affects the efficiency and performance of the light emitting device, so that selection is important. However, phosphorescent host materials, such as 4,4'-N, N'-dicarbazolebiphenyl (CBP), which have been used in the prior art, have higher current efficiency than fluorescent materials, but have high driving voltages, resulting in power efficiency. There was no advantage, and the luminous efficiency and operating life still need improvement.

International Publication Nos. WO 2011/132683 and WO 2011/132684 disclose biscarbazole derivatives having electron and hole transport properties, their use as phosphorescent host materials as electroluminescent devices, and organic electroluminescent devices comprising the same. The disclosed compounds are still not satisfactory in terms of power efficiency and luminous efficiency.

International Publication No. WO 2011/132683 International Publication No. WO 2011/132684

 The present invention was made in response to the above-described demands in the art, and an object thereof is to provide an organic electroluminescent compound having excellent luminous efficiency and power efficiency and an organic electroluminescent device comprising the same.

In order to solve the above technical problem, the present inventors have linked an aromatic ring or an aromatic heterocyclic ring to each other independently by a single bond or by using one or more atoms of N, S, O and C together with a single bond. The present invention has been found to improve the performance of red light emission when a substituent having a structure of the above-described structure is introduced at a specific position of the formula (I).

(I)

In the formula (I)

X ₁ and X ₂ are each independently CH or N;

Ar ₁ And Ar ₂ are each independently hydrogen, substituted or unsubstituted C ₆ -C ₃₀ Aryl group or substituted or unsubstituted 5-60 membered heteroaryl group;

Any one of * has a structure of Formula II, and the other is hydrogen, substituted or unsubstituted C ₆ -C ₃₀ Aryl group or substituted or unsubstituted 5-60 membered heteroaryl group;

≪ RTI ID = 0.0 &

In Chemical Formula II,

L _{1 ,} L ₂ And L ₃ are each independently a single bond or a substituted or unsubstituted C _{6 -} C ₃₀ arylene, and;

A, B, C and D ring are each independently substituted or unsubstituted C ₆ -C ₃₀ An aromatic ring or a substituted or unsubstituted 5-60 membered aromatic heterocycle, wherein at least one of the substituents for the A and D rings may form a fused ring with an adjacent substituent;

E has a structure of Formula III, wherein in Formula III, F and G are each independently substituted or unsubstituted C ₆ -C ₃₀ An aromatic ring or a substituted or unsubstituted 5-60 membered aromatic heterocycle, wherein at least one of the substituents for the rings may form a fused ring with adjacent substituents, Z is a single bond, q is 0 Or 1;

[Formula III]

X and Y are each independently NR ₁ , CR ₂ R ₃ , O or S;

X ₃ is NR ₁ , CR ₂ R ₃ , O or S when r = 0, and N or CR ₄ when r = 1;

R ₁ , R ₂ , R ₃ And R ₄ are each independently hydrogen, substituted or unsubstituted C ₁ -C ₃₀ Alkyl, substituted or unsubstituted C ₆ -C ₃₀ Aryl or substituted or unsubstituted 5-60 membered heteroaryl;

m, n, o, p, r and s are each independently 0 or 1, provided that n + o + p is 1 or more;

Provided that Ar _{1 in} Formula I is phenyl, Ar ₂ is hydrogen, and X ₁ and X ₂ are In the case of N, the case where formula (II) has the following structure is excluded.

The compound of formula (I) of the present invention has better luminous efficiency than the host material of the prior art, leading to an increase in power efficiency. Therefore, when the compound of formula (I) of the present invention is used as a host material, an organic EL device having high efficiency and excellent power consumption can be realized.

Hereinafter, the present invention will be described in detail.

As used herein, “C ₁ -C ₃₀ Alkyl ”means straight or branched chain alkyl having 1 to 30 carbon atoms, preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6 carbon atoms, for example methyl, ethyl , n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

As used herein, “C ₆ -C ₃₀ Aryl ”or“ C ₆ -C ₃₀ Arylene ”means a monocyclic or fused ring radical derived from an aromatic hydrocarbon, and preferably has 6 to 18 ring skeleton carbon atoms. For example, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetrasenyl, fluoranthenyl and the like.

As used herein, “5-60 membered heteroaryl” or “5-60 membered heteroarylene” refers to one or more heteroatoms selected from the group consisting of B, N, O, S, P (═O), Si, and P. It means an aryl group which is contained as an atom and whose remaining ring skeleton atom is carbon, and it is preferable that a ring skeleton atom number is 5-30. The heteroaryl preferably has 1 to 4 heteroatoms, and may be a monocyclic system or a fused ring system condensed with one or more benzene rings. For example, furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxdiazolyl, triazinyl, tetrazinyl, triazolyl Monocyclic heteroaryl such as tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, benzoimidazolyl , Benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindoleyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinolinyl, quinazolinyl, quinoxalin Nyl, carbazolyl, phenoxazinyl, phenantridinyl, benzodioxolyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, benzothiopheno [2,3-c] pyridinyl, benzofuro [2 And fused ring system heteroaryl such as, 3-c] pyridinyl.

As used herein, “C ₆ -C ₃₀ Aromatic ring ”may be a single ring or a fused ring, and C ₆ -C ₁₈ Aromatic rings are preferred. Specific examples include benzene, naphthalene, phenanthrene, anthracene, pyrene, chrysene, acenaphthylene and the like. “5-60 membered aromatic heterocycle” may also be a single ring or a fused ring, preferably 5 to 30 members. Specific examples include pyrazole, imidazole, pyrazine, pyrimidine, indazole, pyrazine, pyrimidine, imidazole, purine, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, perri Midine, phenanthroline, pyrroloimidazole, pyrrolotriazole, pyrazoloimidazole, pyrazolotriazole, pyrazolopyrimidine, pyrazolotriazine, imidazoimidazole, imidazopyridazine, imidazopyridine , Imidazopyrazine, triazolopyridine, benzoimidazole, naphthoimidazole, benzoxazole, naphthooxazole, benzothiazole, naphthothiazole, benzotriazole, tetrazadene, triazine, carbazole, etc. have.

C ₁ -C ₃₀ Alkyl, C ₆ -C ₃₀ Aryl, 5-60 membered heteroaryl, C ₆ -C ₃₀ Aromatic rings, 5-60 membered aromatic heterocycles independently of one another are halogen, cyano, carboxyl, nitro, hydroxy, C ₁ -C ₃₀ Alkyl, HaloC ₁ -C ₃₀ Alkyl, C ₂ -C ₃₀ Alkenyl, C ₂ -C ₃₀ Alkynyl, C ₁ -C ₃₀ Alkoxy, C ₁ -C ₃₀ Alkylthio, C ₃ -C ₃₀ Cycloalkyl, C ₃ -C ₃₀ Cycloalkenyl, 3-7 membered heterocycloalkyl, C ₆ -C ₃₀ Aryl, C ₆ -C ₃₀ aryloxy, C ₆ -C ₃₀ Arylthio, 5-60 membered heteroaryl, C ₆ -C ₃₀ 5-60 membered heteroaryl substituted with aryl, C ₆ -C ₃₀ substituted with 5-60 membered heteroaryl Aryl, triC ₁ -C ₃₀ alkylsilyl, triC ₆ -C ₃₀ arylsilyl, diC ₁ -C ₃₀ alkylC ₆ -C ₃₀ arylsilyl, C ₁ -C ₃₀ alkyldiC ₆ -C ₃₀ arylsilyl, Amino, mono or diC ₁ -C ₃₀ alkylamino, mono or diC ₆ -C ₃₀ arylamino, C ₁ -C ₃₀ alkylC ₆ -C ₃₀ arylamino, C ₁ -C ₃₀ alkylcarbonyl, C _1- C ₃₀ Alkoxycarbonyl, C ₆ -C ₃₀ Arylcarbonyl, diC ₆ -C ₃₀ arylboronyl, diC ₁ -C ₃₀ alkylboronyl, C ₁ -C ₃₀ alkylC ₆ -C ₃₀ arylboronyl, C ₆ -C ₃₀ arC ₁ -C ₃₀ alkyl and C ₁ -C ₃₀ alkylC ₆ -C ₃₀ It may be substituted with one or more selected from the group consisting of aryl, preferably halogen, hydroxy, C ₁ -C ₃₀ Alkyl, C ₁ -C ₃₀ Alkoxy, HaloC ₁ -C ₃₀ Alkyl, C ₆ -C ₃₀ Aryl, 5-60 membered heteroaryl, triC ₁ -C ₃₀ alkylsilyl, triC ₆ -C ₃₀ arylsilyl, diC ₁ -C ₃₀ alkylC ₆ -C ₃₀ arylsilyl, C ₁ -C ₃₀ alkyldiC _6- C ₃₀ arylsilyl, amino, mono or diC ₁ -C ₃₀ alkylamino, mono or diC ₆ -C ₃₀ arylamino and C ₁ -C ₃₀ alkylC ₆ -C ₃₀ arylamino It may be substituted with one or more kinds.

In one embodiment of the present invention, the present invention provides an organic electroluminescent compound represented by any one of the following formula (1).

[Formula 1]

(2)

(3)

[Formula 4]

In the above Chemical Formulas 1 to 4,

X ₁ and X ₂ are each independently CR ₀ or N, and X ₁ and X ₂ At least one of is N,

Ar ₁ , Ar ₂ and Ar ₃ are each independently hydrogen, substituted or unsubstituted C ₆ -C ₃₀ Aryl group, or substituted or unsubstituted 5-60 membered heteroaryl group, preferably hydrogen, substituted or unsubstituted C ₆ -C ₁₈ Aryl group, or a substituted or unsubstituted 5-30 membered heteroaryl group, specific examples of which are hydrogen, phenyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, benzoti Ofeno [2,3-c] pyridinyl, benzofuro [2,3-c] pyridinyl, but are not limited thereto,

L _1, L ₂ and L ₃ is independently a single bond or a substituted or unsubstituted C _6, respectively _- and C ₃₀ arylene, preferably a single bond or a substituted or unsubstituted C ₆ -C ₁₈ ring Arylene, specific examples are single bonds or phenylene, but are not limited thereto,

A, B, C and D ring are each independently substituted or unsubstituted C ₆ -C ₃₀ An aromatic ring or a substituted or unsubstituted 5-60 membered aromatic heterocycle, wherein at least one of the substituents for the A and D rings may form a fused ring with adjacent substituents, preferably substituted or unsubstituted Substituted C ₆ -C ₁₈ Aromatic rings or substituted or unsubstituted 5-30 membered aromatic heterocycles, and specific examples thereof include, but are not limited to, benzene, naphthalene, dibenzofuran, dibenzothiophene, 9,9-dimethylfluorene,

E has a structure of Formula 5, wherein in Formula 5, F and G ring are each independently substituted or unsubstituted C ₆ -C ₃₀ An aromatic ring or a substituted or unsubstituted 5-60 membered aromatic heterocycle, wherein at least one of the substituents for the rings may form a fused ring with adjacent substituents, Z is a single bond, q is 0 Or 1,

[Chemical Formula 5]

X ₃ , X and Y are each independently NR ₁ , CR ₂ R ₃ , O or S,

R ₀ , R ₁ , R ₂ and R ₃ are each independently hydrogen, substituted or unsubstituted C ₁ -C ₃₀ Alkyl, substituted or unsubstituted C ₆ -C ₃₀ Aryl, or substituted or unsubstituted 5-60 membered heteroaryl,

m, n, o and p are each independently 0 or 1, n + o + p is 1 or more,

However, in the above Chemical Formulas 1 to 4, the following compounds are excluded.

In the organic electroluminescent compounds of Formulas 1 to 4, m = 1, n = 1, o = 0, p = 0, L ₂ is a single bond organic electroluminescent compound, m = 0, n = 1, o = Organic electroluminescent compounds with 1 and p = 0, organic electroluminescent compounds with m = 0, n = 1, o = 0 and p = 1, organic electroluminescent fields with m = 0, n = 0, o = 0 and p = 1 An organic electroluminescent compound, such as a luminescent compound, m = 1, n = 1, o = 0, p = 1, and L <_2> is a single bond, etc. are contained.

Examples of the organic electroluminescent compound of Chemical Formula 1 include the following Chemical Formulas 6 to 20.

In Chemical Formulas 6 to 20,

Ar _{1 ,} Ar _{2 ,} L _{1 ,} L ₂ , X and Y are the same as defined in Formula 1,

R ₅ to R ₇ are each independently hydrogen, substituted or unsubstituted C ₆ -C ₃₀ Aryl or substituted or unsubstituted 5-60 membered heteroaryl.

In addition, examples of the organic electroluminescent compound of Chemical Formula 2 include the following Chemical Formulas 21 to 24.

In Chemical Formulas 21 to 24,

Ar _{1 ,} Ar _{2 ,} L ₁ , X and Y are the same as defined in Formula 2,

R ₅ and R ₆ are each independently hydrogen, substituted or unsubstituted C ₆ -C ₃₀ Aryl or substituted or unsubstituted 5-60 membered heteroaryl.

In addition, examples of the organic electroluminescent compound of Chemical Formula 3 include the following Chemical Formulas 25 to 27.

In Chemical Formulas 25 to 27,

Ar _{1 ,} Ar _{2 ,} R ₁ , L ₃ , X and Y are the same as defined in the formula (3).

In addition, examples of the organic electroluminescent compound of Chemical Formula 4 include the following Chemical Formulas 28 to 31.

In Chemical Formulas 28 to 31,

Ar _{1 ,} Ar _{2 ,} X ₃ and Y are the same as defined in the formula (4).

Specific examples of the organic electroluminescent compound of the present invention are as follows, but the present invention is not limited to these compounds.

The compounds of the present invention can be prepared by synthetic methods known in the art. For example, a Suzuki reaction can be used.

According to another aspect of the present invention, the present invention provides an organic electroluminescent device comprising the organic electroluminescent compound.

The organic electroluminescent device includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode.

One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic layer may include a light emitting layer, and may further include one or more layers selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and an interlayer and a hole blocking layer.

As the anode material, indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO), or the like, which is transparent and has excellent conductivity, may be used, and as the material for the cathode, lithium having a small work function is used. , Magnesium, calcium, aluminum, Al: Li, Ba: Li, or Ca: Li may be used.

The organic layer, preferably the light emitting layer, includes at least one compound of formula (I) of the present invention, and the compound of formula (I) may be used as a host material in the light emitting layer. Also, preferably, the light emitting layer further includes one or more phosphorescent dopants. If necessary, one or more other light emitting compounds other than the compound of the formula (I) may be further included.

The dopant used in the organic electroluminescent device of the present invention is not particularly limited, but is preferably a phosphorescent dopant. Phosphorescent dopants include compounds containing copper, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold, preferably metal complexes such as copper complexes, osmium complexes, iridium complexes, platinum complexes, Among them, the iridium complex and the platinum complex are more preferable, and the ortho metallized iridium complex is even more preferable. It can be illustrated by the following compounds D-1 to D-28.

The organic electroluminescent device of the present invention is in addition to the organic material layer containing the compound of formula (I), White light may be generated as a whole by further including at least one light emitting layer including a blue, red or green light emitting compound. Such blue, red or green light emitting compounds are known in the art. Or it may further comprise a yellow or orange light emitting layer as needed.

Moreover, in the organic electroluminescent element of this invention, it is also preferable to arrange | position the mixed region of an electron transfer compound and a reducing dopant, or the mixed region of a hole transfer compound and an oxidative dopant on at least one surface of a pair of electrodes. In this way, since the electron transfer compound is reduced to an anion, it becomes easy to inject and transfer electrons from the mixed region to the light emitting medium. Further, since the hole transport compound is oxidized and becomes a cation, it becomes easy to inject and transport holes from the mixed region into the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds, and preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. Further, a white organic electroluminescent device having two or more light emitting layers can be manufactured using a reductive dopant layer as a charge generation layer.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as &quot; surface layer &quot;) is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Preferable examples of the chalcogenide include SiO _X (1? _X ? 2), AlO _x (1? _X ? 1.5), SiON or SiAlON. Preferred examples of the halogenated metal include LiF, MgF ₂ , CaF ₂ , Rare-earth metals, etc. Preferred examples of the metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

The present invention also provides a composition for an organic electroluminescent device, comprising a first host material and a second host material, wherein the first host material uses the organic electroluminescent compound of the present invention. At this time, the weight ratio of the first host material and the second host material is preferably in the range of 1:99 to 99: 1.

Hereinafter, specific embodiments of the present invention will be described. However, the following examples are merely for illustrating or explaining the present invention in detail, and the present invention is not limited thereto.

The meanings of the abbreviations used in the following examples are as follows.

EtOH: ethanol, DMF: dimethylformamide, EDA: ethylenediamine

EA: ethyl acetate, MC: methylene chloride, THF: tetrahydrofuran

Tol: toluene, rt: room temperature

[Produce Example ]

Produce Example  1: Preparation of Compound 42

Synthesis of Compound 42-3

Compound 42-1 (14g, 48.76mmol), Compound 42-2 (10g, 40.63mmol), K ₂ CO ₃ (13.5g, 97.52mmol) and Pd (PPh ₃ ) ₄ (2.35g, 2.03mmol) toluene 200 After adding to a mixture of ㎖, EtOH 50ml and 50ml purified water and stirred at 90 ~ 100 ℃ for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and then left to obtain a biphasic mixture of an organic phase / aqueous phase. The aqueous phase was removed and the organic phase was concentrated and separated by column chromatography to give compound 42-3 (12 g, 72%).

Synthesis of Compound 42-5

Compound 42-3 (20 g, 49 mmol) and Compound 42-4 (15.6 g, 73.6 mmol) were suspended in 500 mL of DMF, followed by addition of 60% NaH (2.4 g, 58.8 mmol) at room temperature. Stir for 12 hours. The organic phase was extracted with EA and then concentrated under reduced pressure. The concentrate was separated by column chromatography to give compound 42-5 (21 g, 76%).

Synthesis of Compound 42

Compound 42-5 (20 g, 35 mmol), Compound 42-6 (8.3 g, 42 mmol), K ₂ CO ₃ (14.5 g, 105 mmol) and Pd (PPh ₃ ) ₄ (2.02 g, 1.75 mmol) The mixture was added to a mixture of 200 ml of toluene, 40 ml of EtOH, and 40 ml of purified water, followed by stirring at 90˜100 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and then left to obtain a biphasic mixture of an organic phase / aqueous phase. The aqueous phase was removed and the organic phase was concentrated and then separated by column chromatography to give compound 42 (16.4 g, 68%).

Produce Example  2: Preparation of Compound 43

Synthesis of Compound 43-4

Compound 43-3 (14 g, 34.3 mmol) and 1-bromo-4-iodobenzene (48.5 g, 171.4 mmol), CuI (3.3 g, 17.1 mmol), K ₃ PO ₄ (21.8 g, 102.9 mmol) and EDA (2.3 mL, 34.3 mmol) was added to 500 mL of toluene and stirred at reflux for one day. The organic phase was extracted with EA, distilled under reduced pressure and separated by column chromatography with MC / hexane to give compound 43-4 (15.5 g, 80.1%).

Synthesis of Compound 43-5

Compound 43-4 (15.5 g, 27.5 mmol) was dissolved in THF (250 mL) and 2.5 M n-BuLi (17.6 mL, 44 mmol) in hexane was added at −78 ° C. and stirred for an hour. B (OMe) ₃ (12.6 mL, 55 mmol) was added slowly and stirred for 2 hours. After quenching with the addition of 2M HCl, the organic phase was extracted with distilled water and EA. Recrystallization with MC and hexanes gave compound 43-5 (8.7 g, 60%).

Synthesis of Compound 43-7

Compound 43-5 (9.5 g, 18 mmol), Compound 43-6 (7.6 g, 36 mmol), Pd (PPh ₃ ) ₄ (994 mg, 0.86 mmol) and Na ₂ CO ₃ (4.8 g, 45.3 mmol) After dissolving in a mixture of 100 ml of toluene, 20 ml of EtOH, and 20 ml of distilled water, the mixture was stirred at 90 ° C. for 2 hours. The organic phase was extracted with distilled water and EA and then separated by column chromatography with MC and hexane to give compound 43-7 (10 g, 85%).

Synthesis of Compound 43

Compound 43-7 (10 g, 15.45 mmol), Compound 43-8 (4.5 g, 21.2 mmol), Pd (PPh ₃ ) ₄ (890 mg, 0.77 mmol) and K ₂ CO ₃ (6.4 g, 46.35 mmol) After dissolving in a mixture of 80 ml of toluene, 10 ml of EtOH, and 10 ml of distilled water, the mixture was stirred at 90 ° C. for 2 hours. The organic phase was extracted with distilled water and EA and then separated by column chromatography with MC and hexane to give compound 43 (7.45 g, 62%).

Produce Example  3: Preparation of Compound 40

Synthesis of Compound 40

Compound 40-5 (20 g, 35 mmol), compound 40-6 (9.6 g, 42 mmol), K ₂ CO ₃ (14.5 g, 105 mmol) and Pd (PPh ₃ ) ₄ (2.02 g, 1.75 mmol) The mixture was added to a mixture of 200 ml of toluene, 40 ml of EtOH, and 40 ml of purified water, followed by stirring at 90˜100 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and then left to obtain a biphasic mixture of an organic phase / aqueous phase. The aqueous phase was removed and the organic phase was concentrated and then separated by column chromatography to give compound 40 (16.8 g, 67%).

Produce Example  4: Preparation of Compound 95

Synthesis of Compound 95-3

Compound 95-1 (127g, 0.60mol), Compound 95-2 (100g, 0.50mol), K ₂ CO ₃ (159g, 1.50mol) and Pd (PPh ₃ ) ₄ 29g (0.03mol) were added to toluene 3L, EtOH 750 The mixture was added to a mixture of 750 ml and purified water, followed by stirring under reflux for one day. The resulting organic phase was extracted with 2 L of ethyl acetate and washed with 500 ml of distilled water. The organic phase was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography and recrystallization to give compound 95-3 (126g, 87%).

Synthesis of Compound 95-4

Compound 95-3 (126 g, 0.44 mol) was dissolved in 1.1 L of triethylphosphite and stirred under reflux at 150 ° C. After 5 hours, the reaction mixture was cooled to room temperature and distilled under reduced pressure. Silica gel column chromatography and recrystallization to give the compound 95-4 (80g, 71%).

Synthesis of Compound 95-6

Compound 95-4 (10 g, 38.87 mmol) was dissolved in 200 mL of DMF, and 2.3 g (58.30 mmol) of NaH was slowly added thereto. After stirring for 30 minutes, compound 95-5 (7.7 g, 46.64 mmol) is added and then stirred for 4 hours. The mixture was slowly added to 800 ml of distilled water, followed by stirring for 30 minutes. The solid obtained was separated by silica gel column chromatography and recrystallization to give compound 95-6 (8.7 g, 53%).

Synthesis of Compound 95

Compound 95-6 (4g, 9.53mmol), Compound 95-7 (2.2g, 11.43mmol), K ₂ CO ₃ (4g, 28.59mmol) and Pd (PPh ₃ ) ₄ (0.6g, 0.48mmol) toluene 60 ㎖, 15 mL of EtOH and 15 mL of purified water were added to the mixture, followed by stirring under reflux for one day. The organic phase was extracted with 100 ml of ethyl acetate and washed with 50 ml of distilled water. The organic phase was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography and recrystallization to give compound 95 (2.4 g, 47%).

Produce Example  5: Preparation of Compound 96

Synthesis of Compound 96-6

Compound 95-4 (10 g, 38.87 mmol), Compound 96-5 (22 g, 77.74 mmol), CuI (3.7 g, 19.44 mmol), K ₃ PO ₄ (20.6 g, 97.18 mmol) and EDA (2.6 mL, 38.87 mmol) ) Was added to 200 ml of toluene and stirred at 100 ° C. for 24 hours. After the reaction was cooled to room temperature, the organic phase was extracted with 200 ml of ethyl acetate and then washed twice with 50 ml of distilled water. The organic phase was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. Silica gel column chromatography and recrystallization to give the compound 96-6 (12.3g, 77%).

Synthesis of Compound 96-7

Compound 96-6 (12.3 g, 29.83 mmol) was dissolved in 150 mL of THF, and then 17.9 mL (44.75 mmol) of n-BuLi (2.5 M in hexane) was added at -78 ° C. The mixture was stirred at −78 ° C. for 1 hour before the addition of B (Oi-Pr) ₃ compound (10.3 mL, 44.75 mmol). After stirring the whole reaction for 2 hours, the reaction was terminated with 100 mL of NH ₄ Cl, and the organic phase was extracted with 200 mL of ethyl acetate, and then washed with 100 mL of distilled water. The organic phase was dried over MgSO ₄ and the organic solvent was removed under reduced pressure. The obtained solid was separated by recrystallization to give compound 96-7 (8.2 g, 73%).

Synthesis of Compound 96-9

Compound 96-7 (8.2 g, 21.62 mmol), Compound 96-8 (3.9 g, 19.66 mmol), Na ₂ CO ₃ (5.2 g. 49.15 mmol) and Pd (PPh ₃ ) ₄ (1.2 g, 0.98 mmol) The mixture was added to a mixture of 100 ml of toluene, 25 ml of EtOH, and 25 ml of purified water, followed by stirring under reflux for one day. The organic phase was extracted with 100 ml of ethyl acetate and washed with 50 ml of distilled water. The organic phase was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography and recrystallization to give compound 96-9 (4g, 41%).

Synthesis of Compound 96

Compound 96-9 (4g, 8.07mmol), Compound 96-10 (1.8g, 9.68mmol), K ₂ CO ₃ (3.4g, 24.20mmol) and Pd (PPh ₃ ) ₄ (0.5g, 0.41mmol) toluene 60 ml, 15 ml of EtOH and 15 ml of purified water were added to the mixture, followed by stirring under reflux for one day. The organic phase was extracted with 100 ml of ethyl acetate and washed with 50 ml of distilled water. The organic phase was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography and recrystallization to give compound 96 (1.2g, 24%).

Physical properties data of the final compound prepared in Preparation Examples 1 to 5 are as follows.

[ Example  1] The organic Field  Using a luminescent compound OLED  Device fabrication

An OLED device having a structure using the light emitting material of the present invention was fabricated. First, a transparent electrode ITO thin film (15Ω / □) manufactured from OLED glass (manufactured by Samsung-Corning) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol. It was used after. Next, the ITO substrate is mounted on the substrate holder of the vacuum deposition apparatus, and then N ¹ , N ^{1 ′} -([1,1′-biphenyl] -4,4′-diyl) bis ( N 1-(naphthalen- ¹ -yl) -N ⁴ , N ⁴ -diphenylbenzene-1,4-diamine) was added and evacuated until the vacuum in the chamber reached 10 ^-6 torr. Was applied and evaporated to deposit a 60 nm thick hole injection layer on the ITO substrate. Subsequently, N, N'-di (4-biphenyl) -N, N'-di (4-biphenyl) -4,4'-diaminobiphenyl was placed in another cell in the vacuum deposition equipment, and the current was put into the cell. Was applied and evaporated to deposit a 20 nm thick hole transport layer on the hole injection layer. A hole injecting layer and a hole transporting layer were formed, and then a light emitting layer was deposited thereon as follows. Compound 42 as a host in one cell in the vacuum deposition equipment, Compound D-7 as a dopant in each cell, and then the two materials were evaporated at different rates to dope the sum of the two materials to 4% by weight. A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer. Then 2- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole in one cell as an electron transporting layer on the light emitting layer. In each cell, lithium quinolate was added to each other, and the two materials were evaporated at the same rate to be doped so that the sum of the two materials was 50% by weight, thereby depositing an electron transport layer having a thickness of 30 nm. Then, lithium quinolate was deposited to a thickness of 2 nm as an electron injecting layer, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum vapor deposition equipment to fabricate an OLED device. Each compound was purified by vacuum sublimation under 10 ^-6 torr.

As a result, a current of 7.7 mA / cm ² flowed, and red light emission of 1335 cd / m ² was confirmed.

[ Example  2] Using the organic luminescent compound according to the present invention OLED  Device fabrication

An OLED device was manufactured in the same manner as in Example 1, except that Compound 95 was used as a light emitting material and Compound D-7 was used as a dopant.

As a result, a current of 8.6 mA / cm ² flowed, and red light emission of 1554 cd / m ² was confirmed.

[ Example  3] Using the organic luminescent compound according to the present invention OLED  Device fabrication

An OLED device was manufactured in the same manner as in Example 1, except that Compound 96 was used as a light emitting material and Compound D-11 was used as a dopant.

As a result, a current of 15.0 mA / cm ² flowed, and red light emission of 1290 cd / m ² was confirmed.

[ Comparative Example  1] using conventional light emitting material OLED  Device fabrication

As a light emitting material, 4,4'-N, N'-dicarbazole-biphenyl is used as a host, and compound D-11 is used as a dopant, and a light emitting layer having a thickness of 30 nm is deposited on the hole transport layer, and aluminum is used as the hole blocking layer. III) An OLED device was manufactured in the same manner as in Example 1, except that bis (2-methyl-8-quinolinato) 4-phenylphenolate was deposited to a thickness of 10 nm.

As a result, a current of 20.0 mA / cm ² flowed, and red light emission of 1000 cd / m ² was confirmed.

The organic light emitting compounds developed in the present invention can be seen that the red light emitting material shows excellent light emission characteristics compared to the conventional light emitting material. In the conventional device structure, the device using the organic electroluminescent compound according to the present invention as a host material without using a hole blocking layer is excellent in light emission characteristics and can lead to an increase in power efficiency.

Claims (4)

An organic electroluminescent compound represented by any one of the following Chemical Formulas 1 to 4.
[Formula 1]

(2)

(3)

[Formula 4]

In the above Chemical Formulas 1 to 4,
X_One And X₂Are each independently CR₀ Or N, X_One And X₂ At least one of is N;
Ar_One, Ar₂ And Ar₃Are each independently hydrogen, substituted or unsubstituted C₆-C₃₀ Aryl group or substituted or unsubstituted 5-60 membered heteroaryl group;
L_One, L₂ And L₃Are each independently a single bond, substituted or unsubstituted C_{6 -}C₃₀ Arylene;
A, B, C and D ring are each independently substituted or unsubstituted C₆-C₃₀ An aromatic ring or a substituted or unsubstituted 5-60 membered aromatic heterocycle, wherein at least one of the substituents for the A and D rings may form a fused ring with adjacent substituents;
E has a structure of Formula 5, wherein in Formula 5, F and G ring are each independently substituted or unsubstituted C₆-C₃₀ An aromatic ring or a substituted or unsubstituted 5-60 membered aromatic heterocycle, wherein at least one of the substituents for the rings may form a fused ring with adjacent substituents, Z is a single bond, q is 0 Or 1;
[Chemical Formula 5]

X₃, X and Y are each independently NR_One, CR₂R₃, O or S;
R₀, R_One, R₂ And R₃Are each independently hydrogen, substituted or unsubstituted C_One-C₃₀ Alkyl, substituted or unsubstituted C₆-C₃₀ Aryl or substituted or unsubstituted 5-60 membered heteroaryl;
m, n, o and p are each independently 0 or 1 and n + o + p is 1 or more;
However, in the above Chemical Formulas 1 to 4, the following compounds are excluded.

The method of claim 1,
m = 1, n = 1, o = 0, p = 0, L ₂ is a single bond organic electroluminescent compound ;
organic electroluminescent compounds with m = 0, n = 1, o = 1 and p = 0;
organic electroluminescent compounds with m = 0, n = 1, o = 0 and p = 1;
organic electroluminescent compounds with m = 0, n = 0, o = 0 and p = 1; And
an organic electroluminescent compound having m = 1, n = 1, o = 0, p = 1 and L ₂ is a single bond
An organic electroluminescent compound selected from the group consisting of. The organic electroluminescent compound according to claim 1, which is selected from the following compounds.

An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.