KR20140082486A - Novel organic electroluminescent compounds and organic electroluminescent device containing the same - Google Patents

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention has an excellent luminescent efficiency compared with an existing material. The organic electroluminescent device comprising the organic electroluminescent compound has a high current efficiency.

Description

TECHNICAL FIELD The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device containing the same,

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

Among display devices, an electroluminescence device (EL device) is a self-luminous display device having a wide viewing angle, excellent contrast, and a high response speed. In 1987, Eastman Kodak Company first developed an organic EL device using an aromatic diamine and an aluminum complex having a low molecular weight as a material for forming a light emitting layer (Appl. Phys. Lett. 51, 913, 1987].

The most important factor for determining the luminous efficiency in the organic EL device is the luminescent material. As a luminescent material, a fluorescent luminescent material has been widely used, but the development of a phosphorescent luminescent material has been extensively studied in view of the fact that phosphorescent luminescent material can improve luminescent efficiency up to 4 times theoretically compared to a fluorescent luminescent material in the mechanism of electroluminescence . Until now, an iridium (III) complex series has been widely known as a phosphorescent material. Each RGB has bis (2- (2'-benzothienyl) -pyridinate-N, C-3 ') iridium (acetylacetonate Ir (btp) ₂ ], tris (2-phenylpyridine) iridium [Ir (ppy) ₃ ] And bis (4,6-difluorophenylpyridinate-N, C2) picolinato is iridium [Firpic] are known.

The light emitting material may be a mixture of a light emitting material (dopant) and a host material in order to improve color purity, luminous efficiency and stability. When such a light emitting material (dopant) / host material system is used, the selection is important because the host material has a great influence on the efficiency and performance of the light emitting device. In the prior art, 4,4'-N, N'-dicarbazole-biphenyl (CBP) is the most widely known phosphorescent host material. In recent years, Pioneer et al. Of Japan have been using bathocuproine (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenyl phenolate) Balq) as a host material to develop a high-performance organic EL device.

However, the conventional phosphorescent host materials are advantageous from the viewpoint of luminescence properties, but they have the following disadvantages: (1) when the glass transition temperature is low and the thermal stability is low, the material undergoes a high temperature deposition process under vacuum, It changes. (2) In the organic EL device, the power efficiency is inversely proportional to the voltage since it is in the relationship of power efficiency = [(? / Voltage) current efficiency]. However, the organic EL device using the phosphorescent host material has a higher current efficiency (cd / A) than the organic EL device using the fluorescent material, but the driving voltage is also very high, so there is no great advantage in terms of power efficiency (lm / w) . (3) In addition, when used in an organic EL device, it is unsatisfactory in terms of operating life, and luminous efficiency is still required to be improved.

On the other hand, in the organic EL device, as a hole injecting and transporting material, copper phthalocyanine (CuPc), 4,4'-bis [N- (1-naphthyl) -N- phenylamino] biphenyl (NPB) (TPD), 4,4 ', 4 "-tris (3-methylphenylphenyl) -4,4'-diamine Amino) triphenylamine (MTDATA). However, when such a material is used, there is a problem that the quantum efficiency and lifetime of the organic EL device are lowered because when the organic EL device is driven at a high current, Since the thermal stress is generated between the hole injection layers and the lifetime of the device is rapidly lowered due to the thermal stress. Further, since the organic material used for the hole injection layer has a very high hole mobility, The electron-hole charge balance is broken and the quantum efficiency (cd / A) is lowered.

Korean Laid-Open Patent Publication Nos. 2011-0066763 and 2012-0015883 disclose indoleacridine and spiroindoloacridine structures as compounds for organic electroluminescent devices, respectively. However, the organic EL devices including the compounds disclosed in the above documents are still unsatisfactory in terms of power efficiency, luminous efficiency, quantum efficiency and lifetime.

(Patent Document 1) Korean Published Patent Application No. 2011-0066763 (published on June 17, 2011)

(Patent Document 2) Korean Published Patent Application No. 2012-0015883 (published on February 22, 2012)

Accordingly, an object of the present invention is to provide an organic electroluminescent compound having a higher luminous efficiency than conventional materials, and secondly, to provide an organic electroluminescent device having excellent current efficiency including the organic electroluminescent compound.

As a result of intensive studies to solve the above technical problems, the present inventors have found that an amine derivative compound represented by the following formula (1) wherein benzofuran, benzothiophene or indole is fused to indoloacridine or spiroindoloacridine And the present invention has been accomplished.

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 3 -C 30) , Substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted -30 membered heteroaryl, or R < ₁ > and R < ₂ > may be fused to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring;

X is -O-, -S- or -N (R < ₃ >)-;

R ₃ to R ₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, Substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (5-7 membered) heterocycloalkyl, NR ₁₀ R ₁₁ , -SiR ₁₂ R ₁₃ R ₁₄ , -SR ₁₅ , -OR ₁₆ , cyano, nitro or hydroxy;

R ₁₀ to R ₁₆ are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, Substituted or unsubstituted (5- to 7-membered) heterocycloalkyl, or substituted or unsubstituted (C3-C30) cycloalkyl, or together with the adjacent substituent (3-30 membered) monocyclic or polycyclic alicyclic Or an aromatic ring, and the carbon atom of the alicyclic or aromatic ring may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;

a, c, and d are each independently an integer of 1 to 4; when R is an integer of 2 or more, each of R ₄ , R _6, and R ₇ may be the same or different;

b is an integer of 1;

Wherein said heteroaryl and said heterocycloalkyl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;

L ₁ to L ₃ each independently represents a single bond, a substituted or unsubstituted (C 2 -C 30) alkylene, a substituted or unsubstituted (C 6 -C 30) arylene, or a substituted or unsubstituted (5-30 membered) Heteroarylene;

Ar ₁ to Ar ₆ each independently represent a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (5-30 W) or a heteroaryl group, Ar ₁ and Ar _2, Ar ₃ and Ar _4, Ar ₅ and Ar ₆ may be fused to form a substituted or unsubstituted (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring, wherein the carbon atom of the alicyclic or aromatic ring is selected from nitrogen, oxygen and sulfur Lt; / RTI > may be replaced by one or more heteroatoms;

l, m and n are each independently 0 or 1, and l + m + n is 1 or more.

The organic electroluminescent compound according to the present invention has good luminescent properties. The OLED device including the organic electroluminescent compound according to the present invention has excellent luminescence characteristics and current efficiency.

The present invention will now be described in more detail, but this should not be construed as limiting the scope of the present invention.

The present invention relates to an organic electroluminescent compound represented by Formula 1, an organic electroluminescent material including the organic electroluminescent compound, and an organic electroluminescent device including the same.

The compound represented by the formula (1) of the present invention will be described in more detail as follows.

The amine derivative represented by Formula 1 may be represented by Formula 2 below.

(2)

In Formula 2,

X, R ₃ to R ₇ , R ₁₀ to R ₁₆ , L ₁ to L ₃ , Ar ₁ to Ar ₆ , a, c, d and b are the same as defined in Formula 1;

R ₈ is the same as defined for R ₃ in the above formula (1);

R ₉ is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted (5-30 membered) hwandoen (C3-C30) cycloalkyl, substituted or unsubstituted (5-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aralkyl (C1-C30) alkyl, -NR ₁₀ R _11, - SiR ₁₂ R ₁₃ R ₁₄ , -SR ₁₅ , -OR ₁₆ , cyano, nitro, or hydroxy, or together with adjacent substituents may form a (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring , The carbon atom of the alicyclic or aromatic ring may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;

Ar ₇ and Ar ₈ are the same as defined for Ar ₁ in the above formula (1);

L ₄ is the same as the definition of L ₁ in the above formula (1);

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

e and f are each independently an integer of 1 to 4, and when e or f is an integer of 2 or more, each of R ₈ and R ₉ may be the same or different.

In the above formulas (1) and (2), preferably,

R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted (C ₁ -C 30) alkyl, or R ₁ and R ₂ are fused (3-30 membered) to form a monocyclic or polycyclic alicyclic or aromatic ring Forming,

R ₃ to R ₈ are each independently hydrogen; Substituted or unsubstituted (C1-C30) alkyl; (C6-C30) aryl substituted by substituted or unsubstituted (C6-C30) aryl, more preferably (5-30) heteroaryl; Substituted or unsubstituted (5-30 membered) heteroaryl; Or -NR < ₁₀ > R < ₁₁ &

R ₉ together with the adjacent substituents may form a (3-30 membered) monocyclic or polycyclic alicyclic ring;

R ₁₀ and R ₁₁ are each independently a substituted or unsubstituted (C 6 -C 30) aryl or a substituted or unsubstituted (5-30 membered) heteroaryl, more preferably a (C 1 -C 30) alkyl, halogen, -30 membered) heteroaryl, or cyano, and the furnace substituted (C6-C30) aryl, aryl (5-30 membered) heteroaryl substituted by (C6-C30) aryl, or R ₁₀ and R ₁₁ together with an adjacent substituent via ( Lt; / RTI > may form a monocyclic or polycyclic alicyclic or aromatic ring,

L ₁ to L ₄ are each independently a substituted or unsubstituted (C 6 -C 30) arylene, or a substituted or unsubstituted (5-30 membered) heteroarylene;

Ar ₁ to Ar ₈ are each independently (C6-C30) aryl substituted with (C1-C30) alkyl or (C6-C30) aryl, or substituted or unsubstituted (5-30 membered) heteroaryl.

The "(C1-C30) alkyl" described in the present invention means straight chain or branched chain alkyl having 1 to 30 carbon atoms, more preferably having 1 to 10 carbon atoms. Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. The term "(C3-C30) cycloalkyl" as used herein means a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 7 carbon atoms. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. As used herein, the term "(C6-C30) aryl (phenylene)" means a single ring or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein the number of carbon atoms in the ring is 6 to 15. Examples of such aryls include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, , Fluoranthenyl, and the like. As used herein, the term "(5-30) heteroaryl (phenylene)" refers to a heteroaryl group having 5 to 30 ring skeletal atoms and one or more heteroatoms selected from the group consisting of B, N, O, S, P Quot; means an aryl group containing an atom. Here, it is preferable that the number of the ring skeleton atoms is 5 to 15. The number of heteroatoms is preferably 1 to 4, and may be a monocyclic ring system or a fused ring system condensed with at least one benzene ring, and may be partially saturated. In addition, the heteroaryl (phenylene) in the present invention also includes a form in which one or more heteroaryl groups or aryl groups are linked to a heteroaryl group by a single bond. Examples of such heteroaryls include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl , Monocyclic heteroaryl such as triazolyl, tetrazolyl, furanzyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzoimidazolyl, benzothiazolyl, benzothiazolyl, benzoisothiazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, Fused heterocyclic heteroaryl such as norbornyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxaphyl, phenanthridinyl, benzodioxolyl and the like. As used herein, "halogen" includes F, Cl, Br, and I atoms.

Also, in the term "substituted or unsubstituted" described in the present invention, "substituted" means that a hydrogen atom is replaced by another atom or another functional group (ie, a substituent) in a certain functional group. (C ₁ -C 30) alkyl, substituted (C 2 -C 30) alkenyl, substituted (C 3 -C 30) cycloalkyl in the L ₁ to L ₄ , Ar ₁ to Ar ₈ and R ₁ to R ₁₆ of the above- , Substituted (C3-C30) cycloalkenyl, substituted (3-7 membered) heterocycloalkyl, substituted (C6-C30) aryl (Rhen), substituted (5-30 membered heteroaryl (C1-C30) alkyl, (C1-C30) alkyl, (C1-C30) alkoxy, (C3-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (5-30 membered) heteroaryl which is unsubstituted or substituted by (C6-C30) aryl, (C6-C30) aryloxy, (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) -C (C6-C30) arylamino, mono or di (C6-C30) arylamino, (C1-C30) (C 1 -C 30) alkylcarbonyl, (C 1 -C 30) alkoxycarbonyl, (C 6 -C 30) arylcarbonyl, di (C 6 -C 30) arylboronyl, di (C1-C30) alkyl (C6-C30) arylboronyl, (C6-C30) desirable.

Representative examples of the compound according to the present invention include the following compounds.

The compounds according to the present invention can be prepared by synthetic methods known to the person skilled in the art and can be prepared, for example, according to the following Schemes 1 and 2.

[Reaction Scheme 1]

[Reaction Scheme 2]

In the above Reaction Schemes 1 and 2, L ₁ , L ₄ , Ar ₁ , Ar ₂ , Ar ₇ , Ar ₈ , R ₁ to R ₉ , X and a to f are as defined in the above formulas Is halogen.

In a further aspect of the present invention, the present invention provides an organic electroluminescent material comprising an organic electroluminescent compound of Formula 1 and an organic electroluminescent device comprising the above material. The material may be made of the organic electroluminescent compound of the present invention alone, and may further include common materials included in the organic electroluminescent material. An organic electroluminescent device according to the present invention includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer contains at least one compound of the formula (1).

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

The organic electroluminescent compound of Formula 1 of the present invention may be included in the light emitting layer. When used in the light emitting layer, the organic electroluminescent compound of Formula 1 of the present invention may be included as a host material. Preferably, the light emitting layer may further include at least one dopant. If necessary, a compound other than the compound of the formula (1) of the present invention may be further included as a second host material.

The second host material may be any phosphorescent host known in the art, but is preferably selected from the group consisting of compounds represented by the following formulas, from the viewpoint of luminous efficiency.

The second host material may be any phosphorescent host known in the art, but is preferably selected from the group consisting of compounds represented by the following formulas (3) to (5) in view of luminous efficiency.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,

Cz has the following structure,

R ₂₁ to R ₂₄ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Heteroaryl or R ₂₅ R ₂₆ R ₂₇ Si-; R ₂₅ to R ₂₇ are each independently a substituted or unsubstituted (C 1 -C 30) alkyl, or a substituted or unsubstituted (C 6 -C 30) aryl; L ₄ is a single bond, substituted or unsubstituted (C 6 -C 30) arylene, or substituted or unsubstituted (5-30 membered) heteroarylene; M is a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (5-30 membered) heteroaryl; Y ₁ and Y ₂ are -O-, -S-, -N (R ₃₁ ) - or -C (R ₃₂ ) (R ₃₃ ) -, and Y ₁ and Y ₂ are not simultaneously present; R ₃₁ to R ₃₃ are each independently a substituted or unsubstituted (C 1 -C 30) alkyl, a substituted or unsubstituted (C 6 -C 30) aryl, or a substituted or unsubstituted (5-30 membered) ₃₂ and R ₃₃ may be the same or different; each of h and i is independently an integer of 1 to 3, j, k, l and m are each independently an integer of 0 to 4, and when h, i, j, k, l or m is an integer of 2 or more, (Cz-L ₄ ), each (Cz), each R ₂₁ , each R ₂₂ , each R _23, or each R ₂₄ may be the same or different.

Specifically, preferred examples of the host material are as follows.

The dopant included in the organic electroluminescent device of the present invention is preferably at least one phosphorescent dopant. The phosphorescent dopant material to be applied to the organic electroluminescent device of the present invention is not particularly limited, but a complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) And more preferably an ortho-metallated complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and still more preferably an orthometallated iridium complex compound.

The phosphorescent dopant is preferably selected from the group consisting of compounds represented by the following formulas (6) to (8).

[Chemical Formula 7] < EMI ID =

In Formulas 6 to 8, L is selected from the following structures;

R ₁₀₀ is hydrogen, or substituted or unsubstituted (C 1 -C 30) alkyl; R ₁₀₁ to R ₁₀₉ and R ₁₁₁ to R ₁₂₃ are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl unsubstituted or substituted with halogen, cyano, or substituted or unsubstituted (C 1 -C 30) ego; R ₁₂₀ to R ₁₂₃ are adjacent substituents connected to each other to form a fused ring, for example, quinoline formation is possible; R ₁₂₄ to R ₁₂₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl; When R ₁₂₄ to R ₁₂₇ are aryl groups, the adjacent groups are connected to each other to form a fused ring, for example, fluorene formation is possible; R ₂₀₁ to R ₂₁₁ each independently represent hydrogen, deuterium, halogen, or (C 1 -C 30) alkyl unsubstituted or substituted with halogen; o and p are each independently an integer of 1 to 3, and when o or p is an integer of 2 or more, each R ₁₀₀ may be the same or different from each other; n is an integer of 1 to 3;

Specific examples of the phosphorescent dopant material are as follows.

The present invention further provides a material for manufacturing an organic electroluminescent device in a further aspect. The material may comprise a compound of the present invention as a host material. When the compound of the present invention is contained as a host material, the material may further comprise a second host material, wherein the weight ratio of the first host material to the second host material is in the range of 1:99 to 99: 1.

Further, the organic electroluminescent device of the present invention includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes the material for the organic electroluminescence device of the present invention.

The organic electroluminescent device of the present invention may include at least one compound selected from the group consisting of an arylamine compound and a styrylarylamine compound.

In addition, in the organic electroluminescent device of the present invention, in addition to the compound of Formula 1, an organic compound selected from the group consisting of Group 1, Group 2, Group 4, Group 5 transition metal, Lanthanide series metal and d- And the organic layer may further include a light emitting layer and a charge generating layer.

In addition, the organic electroluminescent device of the present invention may emit white light by further including at least one light emitting layer containing a blue, red or green light emitting compound known in the art, in addition to the compound of the present invention. Further, if necessary, it may further include a yellow or orange light emitting layer.

In the organic electroluminescent device of the present invention, one layer (hereinafter referred to as a "surface layer") of a chalcogenide layer, a metal halide layer and a metal oxide layer is formed on at least one inner surface of a 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.

In addition, in the organic electroluminescent device of the present invention, a mixed region of the electron transfer compound and the reducing dopant or a mixed region of the hole transporting compound and the oxidizing dopant is disposed on at least one surface of the pair of electrodes thus fabricated desirable. 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 transporting 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. Also, a white organic light emitting device having two or more light emitting layers can be manufactured using a reducing dopant layer as a charge generating layer.

The formation of each layer of the organic electroluminescent device of the present invention may be performed by a dry film formation method such as vacuum deposition, sputtering, plasma or ion plating, or a wet film formation method such as spin coating, dip coating or flow coating Can be applied.

In the case of the wet film formation method, a thin film is formed by dissolving or dispersing a material forming each layer in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc., And it may be any thing that does not have a problem in the tabernacle.

Hereinafter, the organic electroluminescent compound according to the present invention, the method for producing the same, and the luminescent characteristics of the device will be described with reference to the representative compound of the present invention for a detailed understanding of the present invention.

[Example 1] Preparation of Compound C-57

1-1. Preparation of Compound 3

5 H - benzofuran [3,2- c] carbazole 10.3g (40.10mmol), methyl 2-bromo-5-chlorobenzoate 15g (60.01mmol), copper iodide 3.8g (20.05mmol), diamino-cyclopenten 9.6 mL (80.20 mmol) of hexyl and 17 g (80.20 mol) of potassium phosphate were dissolved in 200 mL of xylene. The mixture was refluxed for 12 hours. The reaction was cooled to room temperature, extracted with 200 mL of ethyl acetate, and the obtained organic layer was washed with 100 mL of distilled water. The organic solvent was removed under reduced pressure. The resulting solid was washed with methanol, filtered and dried. Separating the product obtained by silica gel column chromatography and recrystallization methyl 2 - to give the (5 H-benzofuran [3,2- c] carbazole-5- yl) -5-chlorobenzoate 9.8g (57%) Respectively.

1-2. Synthesis of Compound 4

Methyl 2- (5 H - benzofuran [3,2- c] carbazol-5-1) was dissolved 5-chloro benzoate 8.2g (19.30mmol) in tetrahydrofuran solution 100mL. After stirring the mixture at 0 C for 10 minutes, 16.1 mL (48.30 mmol) of methylmagnesium bromide solution was slowly added dropwise. The reaction was stirred at room temperature for 12 hours and then the reaction was quenched with water. The mixture was extracted with 100 mL of ethyl acetate, and the obtained organic layer was washed with 100 mL of distilled water. The organic solvent was removed under reduced pressure. Separating the resulting liquid by silica gel column chromatography and recrystallization 2- (2- (5 H - benzofuran [3,2- c] carbazole-5- yl) -5-chlorophenyl) propan-2-ol 6.4 g (84%).

1-3. Synthesis of Compound 5

2- (2- (5 H - benzofuran [3,2- c] carbazole-5- yl) -5-chlorophenyl) propan-2-ol 6,4g (16.30mmol), polyphosphoric acid 16.5g (48.90mmol ) And methanesulfonic acid (15.7 g, 163.00 mmol) were dissolved in 410 mL of toluene. The reaction was refluxed and stirred for 3 hours. The reaction was cooled to room temperature, extracted with 400 mL of ethyl acetate, and the obtained organic layer was washed with 200 mL of distilled water. The organic solvent was removed under reduced pressure. The resulting solid was washed with methanol, filtered and dried. Separating the product obtained by silica gel column chromatography and recrystallization from 8-chloro -10,10- dimethyl-benzo -10H- Pew as [3,2- b] indole [3,2,1- de] acridine (63%) of the title compound.

1-4. Synthesis of Compound C-57

Separated by 8-chloro -10,10- dimethyl-benzo -10H- Pew as [3,2- b] indole [3,2,1- de] acridine 4.2g (10.30mmol), (4- ( (12.36 mmol) of palladium acetate, 0.05 g (0.21 mmol) of palladium acetate, 0.5 g (1.24 mmol) of 2-dicyclohexylphosphino-2 ', 6'- dimethoxybiphenyl and 5.5 g (25.75 mmol) of potassium phosphate was dissolved in 100 mL of toluene. The mixture was stirred at reflux for 8 hours. The reaction was cooled to room temperature, extracted with 100 mL of ethyl acetate, and the obtained organic layer was washed with 50 mL of distilled water. The organic solvent was removed under reduced pressure. The resulting solid was washed with methanol, filtered and dried. The obtained product was separated by silica gel column chromatography and recrystallization to obtain 4- (10,10-dimethyl- 10H -benzofura [3,2- b ] indolo [3,2,1- de ] Di-8-yl) -N, N-diphenyl aniline (20%).

[Example 2] Preparation of Compound C-3

2-1. Synthesis of Compound 8

(61.1 mmol) of N-phenyl- [1,1-biphenyl] -4-amine, 21 g (73.32 mmol) of 1-bromo-4-iodobenzene, tris (dibenzylideneacetone) dipalladium 1.5 g (4.89 mmol) of tris (ortho-tolyl) phosphine and 8.8 g (91.65 mmol) of sodium tertiary butoxide were dissolved in 300 mL of toluene. The mixture was stirred at 120 ° C for 3 hours. The reaction was cooled to room temperature, extracted with 200 mL of ethyl acetate, and the obtained organic layer was washed with 200 mL of distilled water. The organic solvent was removed under reduced pressure. The resulting solid was washed with methanol, filtered and dried. The obtained product was separated by silica gel column chromatography and recrystallization to obtain 15 g (61%) of N- (4-bromophenyl) -N-phenyl- [1,1'- biphenyl] -4-amine.

2-2. Synthesis of Compound 10

15 g (37.5 mmol) of N- (4-bromophenyl) -N-phenyl- [1,1'-biphenyl] -4-amine was dissolved in 190 ml of tetrahydrofuran, and then n-butyllithium ) Was added at -78 < 0 > C. The mixture was stirred for 1 hour and then 6.3 mL (56.21 mmol) of trimethoxyborane was added. The whole reaction was stirred at room temperature for 4 hours, then extracted with 200 mL of ethyl acetate, and the obtained organic layer was washed with 100 mL of distilled water. The organic solvent was removed under reduced pressure. The resulting solid was washed with hexane, filtered and dried to give 10 g (73%) of (4 - ([1,1'- biphenyl] -4-yl (phenyl) amino) phenyl) boronic acid.

2-3. Synthesis of Compound C-3

8-chloro--10,10- dimethyl-benzo -10H- Pew [3,2- b] indole as a [3,2,1- de] acridine 6.2g (15.20mmol), (4 - ([1 (18.24 mmol) of palladium acetate, 0.2 g (0.76 mmol) of 2-dicyclohexylphosphino-2 ', 6' 0.8 g (1.82 mmol) of dimethoxybiphenyl and 8.1 g (38 mmol) of potassium phosphate were dissolved in 150 ml of toluene. The mixture was stirred at reflux for 8 hours. The reaction was cooled to room temperature, extracted with 100 mL of ethyl acetate, and the obtained organic layer was washed with 50 mL of distilled water. The organic solvent was removed under reduced pressure. The resulting solid was washed with methanol, filtered and dried. The obtained product was separated by silica gel column chromatography and recrystallization to obtain 4- (10,10-dimethyl- 10H -benzofura [3,2- b ] indolo [3,2,1- de ] Yl) phenyl) -N-phenyl- [l, l ' -biphenyl] -4-amine.

[Device Embodiment 1] Fabrication of OLED element using organic electroluminescent compound according to the present invention

An OLED device having a structure using the light emitting material of the present invention was fabricated. First, a transparent electrode ITO thin film (15 OMEGA / square) obtained from a glass for OLED (manufactured by Samsung Corning) was subjected to ultrasonic cleaning using trichlorethylene, acetone, ethanol and distilled water sequentially and then stored in isopropanol Respectively. Subsequently, an ITO substrate was mounted on a substrate holder of a vacuum deposition apparatus, and N ¹ , N ^{1 '} - ([1,1'-biphenyl] -4,4'-diyl) bis ¹ - (naphthalene- ¹ -yl) -N ⁴ , N ⁴ -diphenylbenzene-1,4-diamine) was introduced into the chamber, and the chamber was evacuated until the degree of vacuum reached 10 ^-6 torr. And evaporated to deposit a 60 nm thick hole injection layer on the ITO substrate. Subsequently, Compound C-3 was placed in another cell in a vacuum vapor deposition apparatus, and a current was applied to the cell to evaporate it, thereby depositing a hole transport layer having a thickness of 20 nm 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. In one of the cells in the vacuum deposition equipment, 9- (4,6-diphenyl-1,3,5-triazin-2-yl) -7,9'-diphenyl-9H, 9'H- '-Bicarbazole and doping another compound with D-1 as a dopant and then evaporating the two materials at different rates to dope the dopant in an amount of 15% by weight based on the total amount of the dopant and the host A 30 nm thick light emitting layer was deposited on the hole transport layer. Subsequently, the following compound E-1 was placed in one cell as an electron transporting layer on the light emitting layer, and lithium quinolate was added to another cell. Then, the two substances were evaporated at the same rate so as to be doped with 50 wt% Whereby an electron transport layer of 30 nm was deposited. 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 8.6 mA / cm < ² > flowed, and green emission of 3980 cd / m < ² > was confirmed.

[Compound E-1]

[Device Embodiment 2] Fabrication of OLED device using organic electroluminescent compound according to the present invention

Compound C-57 as a hole transport layer was deposited to a thickness of 20 nm, and 9-phenyl-3- (4- (9- (4-phenylquinazolin-2-yl) 3-yl) phenyl) -9H-carbazole as a dopant and compound D-37 as a dopant in another cell, and then evaporating the two materials at different rates to obtain a dopant of 3 OLED devices were fabricated in the same manner as in Example 1 except that a light emitting layer with a thickness of 30 nm was deposited on the hole transport layer by doping with an amount of 0.1 wt%

As a result, a current of 8.0 mA / cm < ² > flowed and red luminescence of 1100 cd / m < ² > was confirmed.

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

As a hole transport layer, the following compound R-1 was vapor-deposited to a thickness of 20 nm, 4,4'-N, N'-dicarbazole-biphenyl as a host, and Compound D-15 as a dopant, Except that aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate was deposited to a thickness of 10 nm as a hole blocking layer by vapor deposition of a 30 nm- The OLED device was fabricated in the same manner.

As a result, a current of 10.2 mA / cm ² flowed, and green emission of 3350 cd / m ² was confirmed.

 [Comparative Example 2] OLED element fabrication using conventional light emitting material

As a hole transport layer, the following compound R-1 was vapor-deposited to a thickness of 20 nm, a light emitting layer of 30 nm thickness was deposited on the hole transport layer using CBP as a host and CBP as a dopant, and aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate was deposited to a thickness of 10 nm, an OLED device was fabricated in the same manner as in Example 1.

As a result, a current of 17.4 A / cm ² flowed, and red emission of 1180 cd / m ² was confirmed.

[Compound R-1]

The organic electroluminescent compounds of the present invention are superior in luminous efficiency to conventional materials. The organic electroluminescent device including the organic electroluminescent compound according to the present invention has high current efficiency.

Claims (5)

An organic electroluminescent compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 3 -C 30) , Substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted -30 membered heteroaryl, or R < ₁ > and R < ₂ > may be fused to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring;
X is -O-, -S- or -N (R < ₃ >)-;
R ₃ to R ₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, Substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (5-7 membered) heterocycloalkyl, NR ₁₀ R ₁₁ , -SiR ₁₂ R ₁₃ R ₁₄ , -SR ₁₅ , -OR ₁₆ , cyano, nitro or hydroxy;
R ₁₀ to R ₁₆ are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, Substituted or unsubstituted (5- to 7-membered) heterocycloalkyl, or substituted or unsubstituted (C3-C30) cycloalkyl, or together with the adjacent substituent (3-30 membered) monocyclic or polycyclic alicyclic Or an aromatic ring, and the carbon atom of the alicyclic or aromatic ring may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;
a, c, and d are each independently an integer of 1 to 4; when R is an integer of 2 or more, each of R ₄ , R _6, and R ₇ may be the same or different;
b is an integer of 1;
Wherein said heteroaryl and said heterocycloalkyl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;
L ₁ to L ₃ each independently represents a single bond, a substituted or unsubstituted (C 2 -C 30) alkylene, a substituted or unsubstituted (C 6 -C 30) arylene, or a substituted or unsubstituted (5-30 membered) Heteroarylene;
Ar ₁ to Ar ₆ each independently represent a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (5-30 W) or a heteroaryl group, Ar ₁ and Ar _2, Ar ₃ and Ar _4, Ar ₅ and Ar ₆ may be fused to form a substituted or unsubstituted (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring, wherein the carbon atom of the alicyclic or aromatic ring is selected from nitrogen, oxygen and sulfur Lt; / RTI > may be replaced by one or more heteroatoms;
l, m and n are each independently 0 or 1, and l + m + n is 1 or more. The organic electroluminescent compound according to claim 1, wherein the amine derivative represented by Formula 1 is represented by Formula 2 below.
(2)

In Formula 2,
X, R ₃ to R ₇ , R ₁₀ to R ₁₆ , L ₁ to L _{3 ,} Ar ₁ to Ar ₆ , a, c, d and b are as defined in claim 1;
R ₈ is the same as defined for R ₃ in claim 1;
R ₉ is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted (5-30 membered) hwandoen (C3-C30) cycloalkyl, substituted or unsubstituted (5-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aralkyl (C1-C30) alkyl, -NR ₁₀ R _11, - SiR ₁₂ R ₁₃ R ₁₄ , -SR ₁₅ , -OR ₁₆ , cyano, nitro, or hydroxy, or together with adjacent substituents may form a (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring , The carbon atom of the alicyclic or aromatic ring may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;
Ar ₇ and Ar ₈ are as defined in Ar ₁ in claim 1;
L ₄ is the same as defined for L ₁ in claim 1;
l, m, n and o are each independently 0 or 1, and l + m + n + o is 1 or more;
e and f are each independently an integer of 1 to 4, and when e or f is an integer of 2 or more, each of R ₈ and R ₉ may be the same or different. 3. A compound according to claim 1 or 2, wherein said L ₁ to L ₄ , Ar ₁ to Ar ₈ and R ₁ to R ₁₆ are substituted (C ₁ -C 30) alkyl, substituted (C 2 -C 30) (C3-C30) cycloalkenyl, substituted (3-7 membered) heterocycloalkyl, substituted (C6-C30) aryl (Rhen), substituted (5-30 membered heteroaryl And the substituents of the substituted (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring are each independently selected from the group consisting of deuterium, halogen, cyano, carboxyl, nitro, hydroxy, (C1- (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (5-30 membered) heteroaryl which is unsubstituted or substituted by (C6-C30) aryl, (C6-C30) arylthio, (C6- (C6-C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl (C6-C30) arylsubstituted or unsubstituted with heteroaryl, Ah (C6-C30) arylsilyl, amino, mono or di (C1-C30) alkylamino, mono or di (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboronyl, di (C6-C30) aryl (C6-C30) aryl (C1-C30) Wherein the organic electroluminescent compound is at least one selected from the group consisting of organic electroluminescent compounds and organic electroluminescent compounds. The organic electroluminescent compound according to claim 1, wherein the amine derivative represented by the formula (1) is selected from the following compounds.

An organic electroluminescent device comprising the compound of claim 1.