KR20190096092A - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device using the same. More specifically, the present invention relates to: a novel compound having excellent light emitting capability; and the organic electroluminescent device having improved characteristics such as high luminous efficiency, low driving voltage, long lifespan and the like by comprising the same in at least one of organic matter layers.

Description

Organic light emitting compound and organic electroluminescent device using the same {ORGANIC LIGHT-EMITTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to novel organic compounds that can be used as materials for organic electroluminescent devices and organic electroluminescent devices comprising the same.

Investigating organic electroluminescent (EL) devices that led to blue electroluminescence using anthracene single crystals in 1965, based on observation of Bernanose's organic thin-film emission, followed by Tang in 1987. ) Is an organic electroluminescent device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer. Since then, in order to make a high efficiency, high-life organic electroluminescent device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of specialized materials used therein.

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

The light emitting material may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials required to realize a better natural color according to the light emitting color. In addition, a host / dopant system may be used as the light emitting material in order to increase the light emission efficiency through increase in color purity and energy transfer.

The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the phosphorescent material can theoretically improve the light emission efficiency four times as compared to the fluorescent material, research on phosphorescent host materials as well as phosphorescent dopants has been conducted.

To date, NPB, BCP, Alq ₃ and the like are widely known as hole injection layers, hole transport layers, hole blocking layers, and electron transport layer materials, and anthracene derivatives have been reported as emission layer materials. In particular, phosphorescent materials having advantages in terms of efficiency improvement among the light emitting materials are blue, green, and red dopant materials, such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) _2. Metal complex compounds containing Ir and the like are used. To date, 4,4-dicarbazolybiphenyl (CBP) has shown excellent properties as a phosphorescent host material.

However, the conventional materials have advantages in terms of light emission characteristics, but since the glass transition temperature is low, the thermal stability is poor, and thus, the materials are not satisfactory in terms of lifespan of the organic EL device. Therefore, the development of the material which is more excellent in performance is calculated | required.

Republic of Korea Patent Publication No. 10-2014-0025120 Republic of Korea Patent Publication No. 10-2014-0134884 Republic of Korea Patent Publication No. 10-1347519

An object of the present invention is to provide a novel organic compound which is excellent in thermal stability due to a high glass transition temperature and which can improve the binding force between holes and electrons.

In addition, an object of the present invention is to provide an organic electroluminescent device including the novel organic compound exhibiting a low driving voltage and high luminous efficiency and an improved lifetime.

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

In Chemical Formula 1,

X and Y are O or S,

Z is a direct bond, O or S, m and n are 0 or 1,

L ₁ to L ₄ may be selected from the group consisting of a direct bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms, or they may form a condensed ring with an adjacent group,

A and R ₁ to R ₉ are the same or different from each other, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ to C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl group, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ is selected from the group consisting of an aryl boron group, a C ₆ to C ₆₀ arylphosphanyl group, a C ₆ to C ₆₀ arylphosphinyl group and a C ₆ to C ₆₀ arylamine group; Can form,

Wherein L ₁ to the aryl group and a heteroarylene group, an alkyl group and A and R ₁ to R ₉ in L _4, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, Heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group, arylphosphanyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, amino group, C ₁ ~ C ₄₀ alkyl group , C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl group, C ₆ ~ C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ arylamine group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom of 3 to 40 heterocycloalkyl group, C ₁ to C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl group of boron, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl silyl When substituted or unsubstituted with one or more substituents selected from the group consisting of groups, and when the substituents are plural, they are the same or different from each other.

In addition, the present invention includes an anode, a cathode and one or more organic material layers interposed between the anode and the cathode, at least one of the one or more organic material layers is an organic electroluminescence comprising a compound represented by the formula (1) Provided is an element. Here, the organic material layer including the compound represented by Chemical Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. In this case, a light emitting auxiliary layer may be included between the hole transport layer and the light emitting layer, and the light emitting auxiliary layer may include the compound represented by Chemical Formula 1.

The compound represented by Formula 1 of the present invention may be used as an organic material layer material of the organic electroluminescent device because of excellent thermal stability, carrier transport ability, light emitting ability and the like.

In addition, when the compound represented by Chemical Formula 1 according to an example of the present invention is used as a light emitting auxiliary layer material, an organic electroluminescent device having a lower driving voltage, higher efficiency, and a longer lifetime than conventional light emitting auxiliary layer materials can be manufactured. In addition, the organic EL device may be effectively applied to a full color display panel and the like.

Hereinafter, the present invention will be described in detail.

<New organic compound>

The compound according to the present invention has a large electron donating group (EDG), such as diarylamine or carbazole, bound on one side with dibenzofuran or dibenzothiophene and holes on the other side. The basic skeleton is a structure in which dioxin or thianthrene is combined to improve flow. Various substituents such as an aryl group, a heteroaryl group, etc. are introduced into the basic skeleton, and are represented by Chemical Formula 1.

The compound according to the present invention may have higher hole stability and higher mobility than a structure without dibenzofuran or dibenzothiophene based on dibenzofuran or dibenzothiophene having high hole mobility. In addition, it is possible to further increase the flow of holes in the molecule as a whole by introducing dioxins, which are known to have good holes and electrons, at the ends. Therefore, the hole mobility of the light emitting auxiliary layer is increased, so that the flow of holes and electrons of the device is balanced so that the light emission efficiency of the device can be improved. In addition, the durability and stability of the device is also improved, so that the life of the device can be efficiently increased.

The compound of Formula 1 may be used as an organic material layer material of the organic electroluminescent device, preferably a light emitting auxiliary layer material (red light emitting auxiliary layer material). Furthermore, the full-color organic light emitting panel to which the organic electroluminescent device is applied may also maximize its performance.

In the compound represented by Formula 1, X and Y are O or S. At this time, the compound represented by the formula (1), when X and Y is O, dioxane is bonded to dibenzofuran structure, if X and Y is S, dibenzothiophene structure is bonded structure, When X is O and Y is S, it may have a structure in which thianthrene is bonded to dibenzofuran, and when X is S and Y is O, dioxin may be bonded to dibenzothiophene.

Z is a direct bond, O or S, and m and n are 0 or 1.

The L ₁ to L ₄ is a direct bond, or is selected from the group consisting of C ₆ ~ C ₁₈ arylene group and 5 to 18 hetero arylene group, it is preferable that it is a direct bond or arylene group.

Preferably, L ₁ to L ₄ may be each independently a direct bond or an arylene group of C ₆ to C ₁₈ .

For example, when L ₁ is a direct bond, m is 0 or 1 and n is 0, the compound represented by Formula 1 is 5 to 8 of dibenzofuran (X = O) or dibenzothiophene (X = S). Diarylamine (diarylamine) may be bonded to the position. On the other hand, when L ₁ is C ₆ ~ C ₁₈ arylene, m and n is 1, and when combined with a benzene ring and Z containing R ₂ in the left benzene ring of L ₁ , the compound represented by Formula 1 is di Carbazole, phenoxazine, phenothiazine, etc. may be bonded to positions 5 to 8 of benzofuran (X = O) or dibenzothiophene (X = S). Can be.

Specifically, the compound represented by Chemical Formula 1 may be embodied in any one of the following Chemical Formulas 2 to 5.

In Formulas 2 to 5, X, Y, L ₂ to L ₄ , A, and R ₁ to R ₉ are the same as defined in Formula 1, respectively.

In the compound represented by Formula 1, A and R ₁ to R ₉ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to the 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkylsilyl group, C ₆ to C ₆₀ arylsilyl group, C ₁ to C _{In the} group consisting of ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphanyl group, C ₆ ~ C ₆₀ aryl phosphinyl group and C ₆ ~ C ₆₀ arylamine group Or they may form condensed rings with adjacent groups.

Preferably, R ₁ to R ₉ are the same as or different from each other, and each independently hydrogen, an alkyl group of C ₁ to C ₄₀ , an aryl group of C ₆ to C ₆₀ , a heteroaryl group of 5 to 60 nuclear atoms , C ₆ ~ C ₆₀ aryloxy group, C ₆ ~ C ₆₀ arylsilyl group, C ₆ ~ C ₆₀ aryl boron group and C ₆ ~ C ₆₀ arylamine group, or they are selected from adjacent groups Condensed rings can be formed.

More preferably, R ₁ to R ₉ are the same as or different from each other, and each independently may be selected from the group consisting of hydrogen, a C ₆ ~ C ₆₀ aryl group and a heteroaryl group of 5 to 60 nuclear atoms. .

Also, preferably, A may be a substituent selected from the group consisting of the following structural formulas S1 to S8.

In the above structural formula, * means a site bonded to the formula (1).

Preferably, in the compound represented by Formula 1, X and Y are S or O, Z is a direct bond, O or S, m and n is 0 or 1, L ₁ to L ₃ is a direct bond or It is a C ₆ ~ C ₁₈ arylene group, L ₄ is a direct bond, A is a C ₆ ~ C ₁₈ aryl group, R ₁ to R ₉ may be hydrogen or a C ₆ ~ C ₁₈ aryl group.

The compound represented by Formula 1 according to an example of the present invention described above may be further embodied in compound structures consisting of 1 to 112 illustrated below. However, the compound represented by the formula (1) of the present invention is not limited by those illustrated below.

"Alkyl" in the present invention means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like.

In the present invention, "alkenyl" refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

"Aryl" in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms combined with a single ring or two or more rings. In addition, a form in which two or more rings are attached to each other (pendant) or condensed may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

"Heteroaryl" as used herein means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may be included, and may also include a form in which the two or more rings are condensed with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazolyl, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R 'means an alkyl having 1 to 40 carbon atoms, linear, branched or cyclic structure It may include. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

"Arylamine" in the present invention means an amine substituted with aryl having 6 to 40 carbon atoms.

"Cycloalkyl" as used herein means monovalent substituents derived from monocyclic or polycyclic non-aromatic hydrocarbons having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, and the like.

By "heterocycloalkyl" is meant monovalent substituents derived from non-aromatic hydrocarbons having 3 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S Or a hetero atom such as Se. Examples of such heterocycloalkyl include, but are not limited to, morpholinyl, piperazinyl, and the like.

In the present invention, "alkylsilyl" means silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 5 to 40 carbon atoms.

As used herein, the term “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

The compound of formula 1 according to an example of the present invention can be synthesized in various ways with reference to the synthesis example. Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.

<Organic EL device>

On the other hand, another aspect of the present invention relates to an organic electroluminescent device comprising a compound represented by the above formula (1).

Specifically, the organic electroluminescent device according to the present invention comprises an anode, a cathode and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer It includes a compound represented by the formula (1). In this case, the compound may be used alone, or two or more may be used in combination.

According to an example, the one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, wherein at least one organic material layer may include a compound represented by Formula 1 above. have. Preferably, the organic material layer including the compound of Formula 1 may be a light emitting layer and / or a hole transport layer, more preferably a hole transport layer material. In addition, it is also preferable to include a light emitting auxiliary layer composed of the compound represented by the formula (1) between the hole transport layer and the light emitting layer. In this case, the compound may be a light emitting auxiliary layer material.

The structure of the organic electroluminescent device according to the present invention is not particularly limited, and may be, for example, a structure in which one or more organic layers are stacked between electrodes. Non-limiting examples thereof include (i) an anode, a light emitting layer, a cathode; (Ii) an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode; Or (iii) structures such as an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode.

In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between the electrode and the organic material layer.

The organic electroluminescent device according to the present invention is an organic material layer and an electrode using materials and methods known in the art, except that at least one or more layers of the organic material layer are formed to include the compound represented by Formula 1 of the present invention. It can be prepared by forming a.

The organic material layer including the compound represented by Chemical Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The substrate usable in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, and the like.

In addition, examples of the anode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.

Further, examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or alloys thereof; And multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like.

In addition, the hole injection layer, the hole transport layer, the light emitting layer, the electron injection layer and the electron transport layer is not particularly limited, conventional materials known in the art may be used.

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

[ Preparation  1] Synthesis of Core-1

Diphenylamine (17 g, 100 mmol), 2-bromo-7-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd ₂ (dba) ₃ (4 g, 4 mmol), P (t-Bu) ₃ (2 g, 10 mmol) and sodium tert-butoxide (29 g, 300 mmol) were added to 500 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 500 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain the title compound Core-1 (28 g, 74% yield).

¹ H-NMR: δ 6.63 (m, 4H), 6.81 (m, 2H), 6.86 (d, 1H), 7.20 (m, 4H), 7.40 (s, 1H), 7.50 (d, 1H), 7.73 ( d, 1H), 7.90 (d, 1H), 8.14 (s, 1H)

[ Preparation  2] Synthesis of Core-2

(9-Phenyl-9H-carbazol-2-yl) boronic acid (29 g, 100 mmol), 2-bromo-7-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd (PPh ₃ ) ₄ (4.6 g, 4 mmol) and NaOH (12 g, 300 mmol) were added to 500 ml THF and 250 ml H ₂ O and stirred at 80 ° C. for 12 hours. After the reaction was completed, the resulting solid was filtered. The filtered solid was dissolved in Toluene, recrystallized from Toluene after a Silica filter to obtain the title compound Core-2 (40 g, yield 88%).

¹ H-NMR: δ 7.25 (t, 1H), 7.33 (m, 1H), 7.45 (m, 1H), 7.50 (m, 3H), 7.58 (m, 2H), 7.62 (s, 1H), 7.79 ( d, 1H), 7.86 (d, 1H), 7.94 (d, 1H), 7.99 (d, 1H), 8.00 (m, 2H), 8.14 (s, 1H), 8.18 (d, 1H), 8.55 (d , 1H)

[ Preparation  3] Synthesis of Core-3

(3- (Diphenylamino) phenyl) boronic acid (29 g, 100 mmol), 2-bromo-7-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd (PPh ₃ ) ₄ (4.6 g, 4 mmol) and NaOH (12 g, 300 mmol) were added to 500 ml THF and 250 ml H ₂ O and stirred at 80 ° C. for 12 hours. After the reaction was completed, the resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain the title compound Core-3 (42 g, 91% yield).

¹ H-NMR: δ 6.59 (d, 1H), 6.63 (d, 4H), 6.68 (d, 1H), 6.81 (m, 2H), 7.20 (m, 4H), 7.44 (t, 1H), 7.50 ( s, 1H), 7.86 (d, 1H), 7.99 (d, 1H), 8.00 (d, 2H), 8.14 (s, 1H)

[ Preparation  4] Synthesis of Core-4

(3- (9-Phenyl-9H-carbazol-2-yl) phenyl) boronic acid (36 g, 100 mmol), 2-bromo-7-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd (PPh ₃ ) ₄ (4.6 g, 4 mmol) and NaOH (12 g, 300 mmol) were added to 500 ml THF and 250 ml H ₂ O and stirred at 80 ° C. for 12 hours. After the reaction was completed, the resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain Core-4 (48 g, 89% yield) as the target compound.

¹ H-NMR: δ 7.25 (t, 1H), 7.33 (t, 1H), 7.45 (m, 1H), 7.48 (d, 2H), 7.50 (m, 3H), 7.57 (d, 1H), 7.58 ( m, 2H), 7.62 (s, 1H), 7.79 (d, 1H), 7.86 (d, 1H), 7.94 (d, 1H), 7.99 (d, 1H), 8.00 (d, 2H), 8.14 (s , 1H), 8.18 (d, 1H), 8.55 (d, 1H)

[ Preparation  5] Synthesis of Core-5

Diphenylamine (17 g, 100 mmol), 2-bromo-8-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd ₂ (dba) ₃ (4 g, 4 mmol), P (t-Bu) ₃ (2 g, 10 mmol) and sodium tert-butoxide (29 g, 300 mmol) were added to 500 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 500 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene, and then recrystallized with Toluene after Silica filter to obtain the target compound Core-5 (28 g, 74% yield).

¹ H-NMR: δ 6.63 (m, 4H), 6.81 (m, 2H), 6.86 (d, 1H), 7.20 (m, 4H), 7.40 (s, 1H), 7.48 (d, 1H), 7.73 ( d, 1H), 7.92 (d, 1H), 8.24 (s, 1H)

[ Preparation  6] Synthesis of Core-6

(9-Phenyl-9H-carbazol-2-yl) boronic acid (29 g, 100 mmol), 2-bromo-8-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd (PPh ₃ ) ₄ (4.6 g, 4 mmol) and NaOH (12 g, 300 mmol) were added to 500 ml THF and 250 ml H ₂ O and stirred at 80 ° C. for 12 hours. After the reaction was completed, the resulting solid was filtered. The filtered solid was dissolved in Toluene, recrystallized from Toluene after a Silica filter to obtain the title compound Core-6 (36 g, yield 78%).

¹ H-NMR: δ 7.25 (t, 1H), 7.33 (m, 1H), 7.45 (m, 1H), 7.48 (d, 1H), 7.50 (m, 2H), 7.58 (m, 2H), 7.62 ( s, 1H), 7.79 (d, 1H), 7.86 (d, 1H), 7.92 (d, 1H), 7.94 (d, 1H), 8.00 (m, 2H), 8.18 (d, 1H), 8.24 (s , 1H), 8.55 (d, 1H)

[ Preparation  7] Synthesis of Core-7

(3- (Diphenylamino) phenyl) boronic acid (29 g, 100 mmol), 2-bromo-8-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd (PPh ₃ ) ₄ (4.6 g, 4 mmol) and NaOH (12 g, 300 mmol) were added to 500 ml THF and 250 ml H ₂ O and stirred at 80 ° C. for 12 hours. After the reaction was completed, the resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain the title compound Core-7 (39 g, 85% yield).

¹ H-NMR: δ 6.59 (d, 1H), 6.63 (d, 4H), 6.68 (d, 1H), 6.81 (m, 2H), 7.20 (m, 4H), 7.44 (t, 1H), 7.48 ( d, 1H), 7.86 (d, 1H), 7.92 (d, 1H), 8.00 (d, 2H), 8.24 (s, 1H)

[ Preparation  8] Synthesis of Core-8

(3- (9-Phenyl-9H-carbazol-2-yl) phenyl) boronic acid (36 g, 100 mmol), 2-bromo-8-chlorodibenzo [b, d] thiophene (30 g, 100 mmol), Pd (PPh ₃ ) ₄ (4.6 g, 4 mmol) and NaOH (12 g, 300 mmol) were added to 500 ml THF and 250 ml H ₂ O and stirred at 80 ° C. for 12 hours. After the reaction was completed, the resulting solid was filtered. The filtered solid was dissolved in toluene and recrystallized with toluene after Silica filter to obtain Core-8 (45 g, yield 83%) as a target compound.

¹ H-NMR: δ 7.25 (t, 1H), 7.33 (t, 1H), 7.45 (m, 1H), 7.48 (m, 3H), 7.50 (m, 2H), 7.57 (d, 1H), 7.58 ( m, 2H), 7.62 (s, 1H), 7.79 (d, 1H), 7.86 (d, 1H), 7.92 (d, 1H), 7.94 (d, 1H), 8.00 (d, 2H), 8.18 (d , 1H), 8.24 (s, 1H), 8.55 (d, 1H)

[ Synthesis Example  1] Synthesis of Compound 1

Core-1 (3.9 g, 10.0 mmol), N-phenyldibenzo [b, e] [1,4] dioxin-2-amine (2.8 g, 10.0 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol) , P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain Compound 1 (5.8 g, yield 94%) as a target compound.

[LCMS]: 624

[ Synthesis Example  2] Synthesis of Compound 2

Core-1 (3.9 g, 10.0 mmol), N-([1,1'-biphenyl] -4-yl) dibenzo [b, e] [1,4] dioxin-2-amine (3.5 g, 10.0 mmol) , Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol), P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene at 110 ° C. Stir for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene, and then recrystallized with Toluene after Silica filter to obtain Compound 2 (5.9 g, 84% yield) as a target compound.

[LCMS]: 700

[ Synthesis Example  3] Synthesis of Compound 13

Core-2 (4.6 g, 10.0 mmol), N-phenyldibenzo [b, e] [1,4] dioxin-2-amine (2.8 g, 10.0 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol) , P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene, and then recrystallized with Toluene after Silica filter to obtain compound 13 (5.9 g, yield 84%) as a target compound.

[LCMS]: 698

[ Synthesis Example  4] Synthesis of Compound 14

Core-2 (4.6 g, 10.0 mmol), N-([1,1'-biphenyl] -4-yl) dibenzo [b, e] [1,4] dioxin-2-amine (3.5 g, 10.0 mmol) , Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol), P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene at 110 ° C. Stir for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain compound 14 (6.0 g, yield 86%) as a target compound.

[LCMS]: 774

[ Synthesis Example  5] Synthesis of Compound 19

Core-3 (4.6 g, 10.0 mmol), N-([1,1'-biphenyl] -4-yl) dibenzo [b, e] [1,4] dioxin-2-amine (3.5 g, 10.0 mmol) , Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol), P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene at 110 ° C. Stir for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain compound 19 (6.2 g, yield 79%) as a target compound.

[LCMS]: 776

[ Synthesis Example  6] Synthesis of Compound 20

Core-4 (5.4 g, 10.0 mmol), N-phenyldibenzo [b, e] [1,4] dioxin-2-amine (2.8 g, 10.0 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol) , P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain compound 20 (6.2 g, yield 81%) as a target compound.

[LCMS]: 774

[ Synthesis Example  7] Synthesis of Compound 33

Core-5 (3.9 g, 10.0 mmol), N-phenyldibenzo [b, e] [1,4] dioxin-2-amine (2.8 g, 10.0 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol) , P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. After filtering, the solid was dissolved in Toluene, and then recrystallized with Toluene after a Silica filter to obtain compound 33 (5.0 g, yield 81%) as a target compound.

[LCMS]: 624

[ Synthesis Example  8] Synthesis of Compound 34

Core-5 (3.9 g, 10.0 mmol), N-([1,1'-biphenyl] -4-yl) dibenzo [b, e] [1,4] dioxin-2-amine (3.5 g, 10.0 mmol) And Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol), P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) in 50 ml toluene at 110 ° C. Stir for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain Compound 34 (6.0 g, yield 86%) as a target compound.

[LCMS]: 700

[ Synthesis Example  9] Synthesis of Compound 45

Core-6 (4.6 g, 10.0 mmol), N-phenyldibenzo [b, e] [1,4] dioxin-2-amine (2.8 g, 10.0 mmol), Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol) , P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain Compound 45 (5.5 g, Yield 79%) as the target compound.

[LCMS]: 698

[ Synthesis Example  10] Synthesis of Compound 46

Core-6 (4.6 g, 10.0 mmol), N-([1,1'-biphenyl] -4-yl) dibenzo [b, e] [1,4] dioxin-2-amine (3.5 g, 10.0 mmol) , Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol), P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene at 110 ° C. Stir for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain Compound 46 (5.4 g, yield 70%) as a target compound.

[LCMS]: 774

[ Synthesis Example  11] Synthesis of Compound 51

Core-7 (4.6 g, 10.0 mmol), N-([1,1'-biphenyl] -4-yl) dibenzo [b, e] [1,4] dioxin-2-amine (3.5 g, 10.0 mmol) , Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol), P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene at 110 ° C. Stir for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain compound 51 (6.3 g, yield 81%) as a target compound.

[LCMS]: 776

[ Synthesis Example  12] Synthesis of Compound 52

Core-8 (5.4 g, 10.0 mmol), N-phenyldibenzo [b, e] [1,4] dioxin-2-amine (2.8 g, 10.0 mmol) and Pd ₂ (dba) ₃ (0.4 g, 0.4 mmol) , P (t-Bu) ₃ (0.2 g, 1.0 mmol) and sodium tert-butoxide (2.9 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, 50 ml of water was added and stirred. The resulting solid was filtered. The filtered solid was dissolved in Toluene and recrystallized with Toluene after Silica filter to obtain compound 20 (6.1 g, yield 79%) as a target compound.

[LCMS]: 774

Example 1 Fabrication of Red Organic EL Device

Compound 1 synthesized in Synthesis Example 1 was subjected to high purity sublimation purification by a conventionally known method, and then a red organic EL device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech). The substrate was transferred to.

On this prepared ITO transparent electrode, m-MTDATA (60 nm) / TCTA (80 nm) / Compound 1 (40 nm) / CBP + 10% (piq) ₂ Ir (acac) (300 nm) / BCP (10 nm ) / Alq3 (30 nm) / LiF (1 nm) / Al (200 nm) was laminated in order to prepare an organic EL device.

[Examples 2 to 12] Fabrication of Red Organic EL Devices

Except for using the compound 2, 13, 14, 19, 20, 33, 34, 45, 46, 51, 54 synthesized in Synthesis Examples 2 to 12 instead of the compound 1 used in Example 1, The red organic electroluminescent device was manufactured in the same manner as 1.

Comparative Example 1 Fabrication of Red Organic EL Device

A red organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound A was used instead of Compound 1 used in Example 1 as a red light-emitting auxiliary layer material.

Comparative Example 2 Fabrication of Red Organic EL Device

A red organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound B was used instead of Compound 1 used in Example 1 as a red light-emitting auxiliary layer material.

The structures of m-MTDATA, TCTA, CBP, Ir (piq) ₂ acac, Compound A and Compound B used in Examples 1 to 12 and Comparative Examples 1 and 2 are as follows.

[Evaluation Example]

For each of the red organic electroluminescent devices fabricated in Examples 1 to 12 and Comparative Examples 1 and 2, driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below. Shown in

Sample Luminous auxiliary layer Driving voltage
(V) EL peak
(nm) Current efficiency
(cd / A) Example 1 One 4.5 620 45.1 Example 2 2 4.3 620 46,2 Example 3 13 4.5 620 44.1 Example 4 14 4.5 620 44.3 Example 5 19 4.6 620 45.1 Example 6 20 4.7 620 45,2 Example 7 33 4.5 620 44.3 Example 8 34 4.6 620 44.1 Example 9 45 4.5 620 46.1 Example 10 46 4.6 620 47.1 Example 11 51 4.6 620 49.8 Example 12 54 4.7 620 44.3 Comparative Example 1 A 5.3 620 35.2 Comparative Example 2 B 5.2 620 37.1

As shown in Table 1, the red organic electroluminescent devices of Examples 1 to 12, which use the compounds represented by Formula 1 (Compounds 1 to 112) according to the present invention as the light emitting auxiliary layer material, are conventionally similar structural compounds. It can be seen that the driving voltage and the current efficiency are better than those of the red organic electroluminescent devices of Comparative Examples 1 and 2 using A and Compound B as light emitting auxiliary layer materials.

Claims (10)

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

In Chemical Formula 1,
X and Y are O or S,
Z is a direct bond, O or S, m and n are 0 or 1,
L ₁ to L ₄ are selected from the group consisting of a direct bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms,
A and R ₁ to R ₉ are the same or different from each other, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ to C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl group, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ is selected from the group consisting of an aryl boron group, a C ₆ to C ₆₀ arylphosphanyl group, a C ₆ to C ₆₀ arylphosphinyl group and a C ₆ to C ₆₀ arylamine group; Can form,
Wherein L ₁ to the aryl group and a heteroarylene group, an alkyl group and A and R ₁ to R ₉ in L _4, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, Heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group, arylphosphanyl group, and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, amino group, C ₁ ~ C ₄₀ An alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₆ to C ₆₀ aryl group, a nuclear atom having 5 to 60 heteroaryl groups, a C ₆ to C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkylsilyl group, C group ₁ ~ C ₄₀ alkyl, boron, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ aryl chamber of the C ₆₀ of the If a group is unsubstituted or substituted by one substituent at least one selected from the group consisting, of a plurality of the substituents, which are the same or different from each other. The method of claim 1,
The compound represented by Formula 1 is a compound represented by any one of the following Formula 2 to Formula 7:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5,
X, Y, L ₂ to L ₄ , A and R ₁ to R ₉ are the same as defined in Chemical Formula 1, respectively. The method of claim 1,
L ₁ to L ₄ are each independently a direct bond or a C ₆ ~ C ₁₈ arylene group. The method of claim 1,
R ₁ to R ₉ are the same as or different from each other, and each independently hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, a nuclear atom having 5 to 60 heteroaryl groups, and C ₆ to C ₆₀ aryloxy group, C ₆ ~ C ₆₀ arylsilyl group, C ₆ ~ C ₆₀ aryl boron group and C ₆ ~ C ₆₀ arylamine group, or they form a condensed ring with adjacent groups Compound that can. The method of claim 1,
A is a compound selected from the group consisting of the following structural formula S1 to S8.

In the above structural formula,
* Means a site bonded to the formula (1). The method of claim 1,
In Formula 1, X and Y are S or O, Z is a direct bond, O or S, m and n is 0 or 1, L ₁ to L ₃ is a direct bond or an arylene group of C ₆ ~ C ₁₈ And L ₄ is a direct bond, A is a C ₆ -C ₁₈ aryl group, and R _1- R ₉ are hydrogen or a C ₆ -C ₁₈ aryl group. The method of claim 1,
Compound represented by Formula 1 is selected from the group consisting of compounds represented by 1 to 112.

The method of claim 1,
The compound represented by Formula 1 is a compound represented by the following compound 1, 2, 13, 14, 19, 20, 33, 34, 45, 46, 51 or 54.

An anode, a cathode, and one or more organic material layers interposed between the anode and the cathode;
At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 to 8. The method of claim 9,
The organic material layer including the compound is selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer and an electron injection layer.