KR102032971B1 - Novel dibenzoazasilane compounds, a process for their preparation and organic electroluminescent devices comprising the same - Google Patents

Abstract

The present invention relates to a novel dibenzoazacillin compound, a method for preparing the same, and an organic electroluminescent device including the same. The dibenzoazacillin compound of the present invention has a specific electron donor and a specific electron acceptor in a molecule, and employs the same. The organic EL device has excellent luminous efficiency and color purity.

Description

Novel dibenzoazasilane compounds, a process for their preparation and organic electroluminescent devices comprising the same

The present invention relates to a novel dibenzoazacillin compound, a method for preparing the same, and an organic electroluminescent device including the same, and more particularly, to a dibenzoazacillin compound exhibiting thermally activated delayed fluorescence (TADF); It relates to a manufacturing method thereof and an organic electroluminescent device comprising the same.

Recently, as the development of the information and communication industry is accelerated, higher performance is required in the field of display devices, which is one of the most important fields.

Such display devices can be classified into emission type and non-emission type, and the display elements belonging to the emission type include a cathode ray tube (CRT), an electroluminescence scene (ELD), and an electroluminescent diode (Light Emitting Diode): LED), Plasma Device Panel (PDP), and the like, and non-light emitting display devices include Liquid Crystal Display (LCD).

In general, the organic electroluminescence phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electroluminescent device using an organic electroluminescent phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. In this case, the organic material layer is often formed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

As mentioned above, in order to meet the high performance, studies on various configurations of the organic electroluminescent device as described above are being conducted. The core is a light emitting material included in the light emitting layer.

Recently, interest in thermally activated delayed fluorescence (TADF) materials, which are evaluated as materials for 3rd generation OLEDs, has been increasing following fluorescent materials and phosphors as light emitting materials. The thermally activated delayed fluorescence (TADF) material is a material that converts triplet excitons to singlet and converts it to light, unlike a phosphor that converts singlet excitons to triplet and converts to light. It shows fluorescence characteristics and theoretically can convert both singlet and triplet excitons to light, which makes it possible to achieve 100% internal quantum efficiency, thus overcoming the life and efficiency limitations of blue and red phosphorescent materials. The research on this is being activated.

Representative mechanisms for the above-described thermally activated delayed fluorescence (TADF) are triplet-triplet annihilation (TTA) and triplet through reverse intersystem crossing (RISC). Is due to the conversion to singlet. At this time, the TTA is currently used for high efficiency fluorescence blue and green devices, but since the triplet is extinguished and one singlet is formed, there is a low internal quantum efficiency. RISC, on the other hand, has the advantage that theoretically all triplets can be converted to singlet, so that all excitons can be converted to light, thereby realizing high internal quantum efficiency.

Therefore, there is a need for a study of novel compounds exhibiting thermally activated delayed fluorescence.

Adv. Mater. 2009, 21, 4802-4806

SUMMARY OF THE INVENTION An object of the present invention is to provide a dibenzoazacillin compound having low optical stability and energy band gap and improved optical properties, and a method for preparing the same.

In addition, the present invention provides an organic electroluminescent device having high thermal stability, excellent efficiency and color purity by employing the dibenzoazacillin compound of the present invention.

In order to achieve the above object, the present inventors have been developing a new compound that exhibits thermally activated delayed fluorescence (TADF) through reverse intersystem crossing (RISC), a dibenzoazacillin compound, In particular, dibenzo [b, e] [1,4] azacillin (dibenzo [b, e] [1,4] azasiline) is a basic skeleton of dibenzoazacillin, not the N-site of dibenzoazacillin. The introduction of the respective electron acceptor (acceptor) in the benzene ring of the surprisingly improved thermal stability and color purity was found to complete the present invention.

That is, the present invention is employed in an organic electroluminescent device to provide a dibenzoazacillin compound having an amazing color purity, the dibenzoazacillin compound of the present invention is represented by the following formula (1).

[Formula 1]

(In Formula 1,

R ¹ is (C6-C30) aryl;

Ar ¹ and Ar ² are independently of each other (C6-C30) arylene;

The aryl of R ^{1 and} the arylene of Ar ¹ and Ar ² may be further substituted with any one or more selected from (C 1 -C 30) alkyl and (C 1 -C 30) alkoxy.)

Preferably Ar ¹ and Ar ² in Formula 1 according to an embodiment of the present invention may be the same as each other (C6-C18) arylene, more preferably Ar ¹ and Ar ² are the same as each other (C1-C30) Phenylene unsubstituted or substituted with (alkyl), naphthalenylene unsubstituted or substituted with (C1-C30) alkyl, or anthracenylene unsubstituted or substituted with (C1-C30) alkyl.

In view of having improved thermal stability, color purity and efficiency, preferably, in Formula 1, R ¹ is phenyl; Ar ¹ and Ar ² may be identically substituted with (C 1 -C 10) alkyl or phenylene unsubstituted.

Dibenzoazacillin compound represented by Formula 1 according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

In another aspect, the present invention provides a method for producing a dibenzoazacillin compound represented by the formula (1) of the present invention, the method for producing a dibenzoazacillin compound, by reacting the following formula 11 and the formula (12) Preparing a dibenzoazacillin compound.

[Formula 1]

[Formula 11]

[Formula 12]

(In Formula 1, Formula 11 and Formula 12,

R ¹ is (C6-C30) aryl;

Ar ¹ and Ar ² are independently of each other (C6-C30) arylene;

X is halogen;

The aryl of R ^{1 and} the arylene of Ar ¹ and Ar ² may be further substituted with any one or more selected from (C 1 -C 30) alkyl and (C 1 -C 30) alkoxy.)

In another aspect, the present invention provides an organic electroluminescent device comprising a dibenzoazacillin compound according to an embodiment of the present invention.

Preferably, the dibenzoazacillin compound included in the organic electroluminescent device according to an embodiment of the present invention may be included in the light emitting layer of the organic electroluminescent device.

The dibenzoazacillin compound of the present invention includes dibenzoazacillin, which is a specific electron donor, and a specific electron acceptor at the same time in a molecule, thereby exhibiting an amazingly improved color purity and lifespan.

In particular, the dibenzoazacillin compound of the present invention has excellent orientation by introducing a specific electron acceptor at a specific position of the dibenzoazacillin skeleton, which is an electron donor, and has an improved color purity without degrading the efficiency of the organic electroluminescent device including the same. .

Therefore, the organic electroluminescent device of the present invention has improved color purity, high quantum efficiency, low power consumption, and long life by including dibenzoazacillin compound as a hole transport material, a light emitting material (phosphorescent host), especially a thermally activated delayed fluorescent dopant material. .

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the color coordinate of the organic electroluminescent element which employ | adopted the compound of Example 1, the comparative example 1, and the comparative example 2 of this invention.

The present invention provides a novel dibenzoazacillin compound that is excellent in thermal stability and can improve the stability, luminous efficiency and color purity of an organic electroluminescent device including the same by introducing a specific electron acceptor at a specific position of the central skeleton. By doing so, the dibenzoazacillin compound of the present invention is represented by the following formula (1).

[Formula 1]

(In Formula 1,

R ¹ is (C6-C30) aryl;

Ar ¹ and Ar ² are independently of each other (C6-C30) arylene;

The aryl of R ^{1 and} the arylene of Ar ¹ and Ar ² may be further substituted with any one or more selected from (C 1 -C 30) alkyl and (C 1 -C 30) alkoxy.)

및

)로 이를 포함하는 유기 전계 발광 소자는 현저하게 향상된 전기적 특성을 가진다.In the dibenzoazacillin compound of the present invention, a specific electron acceptor is introduced into the benzoic site of the dibenzoazacillin instead of the N-site of the dibenzoazacillin skeleton, which is an electron donor, and the introduced electron acceptor is also a functional group having a specific structure (

And

The organic electroluminescent device including the same has a significantly improved electrical characteristics.

Specifically, the dibenzoazacillin compound of the present invention includes an intramolecular electron donor and an electron acceptor at the same time, but has an amazingly improved color purity, thermal stability and efficiency by introducing an electron donor having a different structure from the conventional site into a specific site.

Furthermore, the dibenzoazacillin compound of the present invention has respective electron donors on both sides of the central dibenzoazacillin skeleton, so that the organic electroluminescent device including the same has excellent color coordinates with excellent orientation.

Ar ¹ and Ar ² in the formula (1) according to an embodiment of the present invention in terms of having a better color purity may be the same as each other (C6-C18) arylene.

및

)를 도입하되 전자수용체(디벤조아자실린)와 전자공여체 사이에 링크로 (C6-C18)아릴렌을 도입함으로써 전자공여체와 전자수용체 사이의 이면각을 증가시켜 π-컨쥬게이션 길이가 줄어 수평방향 방출 쌍극자의 비율을 증가시키게 됨으로써 이를 포함하는 유기 전계 발광 소자는 보다 우수한 색순도를 가지는 청색을 방출할 수 있는 것으로 판단된다.Dibenzoazacillin compound according to an embodiment of the present invention is not the N-position of each of the central backbone dibenzoazacillin, each electron donor (

And

), But by introducing (C6-C18) arylene as a link between the electron acceptor (dibenzoazacillin) and the electron donor, increasing the backside angle between the electron donor and the electron acceptor, reducing the π-conjugation length. By increasing the ratio of the emission dipole, it is determined that the organic EL device including the same may emit blue color having better color purity.

In this respect, preferably Ar ¹ and Ar ² are the same as each other, phenylene unsubstituted or substituted with (C1-C30) alkyl, naphthalenylene unsubstituted or substituted with (C1-C30) alkyl, or (C1-C30). Anthracenylene unsubstituted or substituted with alkyl, more preferably phenylene unsubstituted or substituted with (C1-C10) alkyl, naphthalenylene unsubstituted or substituted with (C1-C10) alkyl, or ( Or anthracenylene unsubstituted or substituted with C1-C10) alkyl, more preferably phenylene unsubstituted or substituted with (C1-C10) alkyl.

Preferably, the dibenzoazacillin compound represented by Formula 1 according to an embodiment of the present invention may be represented by the following Formula 2.

[Formula 2]

(In Chemical Formula 2)

R ¹¹ to R ¹² are each independently hydrogen or (C 1 -C 10) alkyl.)

In the dibenzoazacillin compound represented by Formula 2 according to an embodiment of the present invention, an electron donor is introduced at a specific position of the dibenzoazacillin skeleton, which is an electron acceptor, and these are converted into a specific linker, phenylene or (C1-C10) alkyl. The introduction of substituted phenylenes prevents the complete separation of HOMO and LUMO at energy levels and shortens the π-conjugation on the electron donor and the electron acceptor, thereby enabling deep blue-green emission of the organic electroluminescent device employing it. It seems to be.

Preferably R ¹¹ to R ¹² in Formula 2 according to an embodiment of the present invention may be independently of each other hydrogen or (C1-C5) alkyl.

That is, Chemical Formula 2 according to an embodiment of the present invention has an electron donor at both benzo sites of the dibenzoazacillin skeleton, which is an electron acceptor, and is substituted with a specific linker (C1-C5) alkyl. By introducing unsubstituted phenylene, it is possible to manufacture an organic electroluminescent device excellent in durability and color purity without degrading optical properties such as efficiency.

Dibenzoazacillin compound represented by Formula 1 according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

Substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described herein include all straight or pulverized forms, having 1 to 30 carbon atoms, preferably 1 to 20, more preferably 1 To 10 carbon atoms.

In addition, "aryl" as described herein is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7 ring atoms, preferably 5 or 6 ring atoms, as appropriate for each ring. It includes a ring system, a form in which a plurality of aryl is connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

The "substituted" functional groups described herein may be, but are not limited to, (C1-C30) alkyl and (C1-C30) alkoxy.

In another aspect, the present invention provides a method for producing a dibenzoazacillin compound represented by the formula (1) of the present invention.

The method for preparing a dibenzoazacillin compound of the present invention includes the step of preparing the following Chemical Formula 1 by reacting the following Chemical Formula 12 from Chemical Formula 11 in the presence of a catalyst.

[Formula 1]

[Formula 11]

[Formula 12]

(In Formula 1, Formula 11 and Formula 12,

R ¹ is (C6-C30) aryl;

Ar ¹ and Ar ² are independently of each other (C6-C30) arylene;

X is halogen;

The aryl of R ^{1 and} the arylene of Ar ¹ and Ar ² may be further substituted with any one or more selected from (C 1 -C 30) alkyl and (C 1 -C 30) alkoxy.)

The catalyst according to an embodiment of the present invention may be a paradium catalyst, specifically Tris (dibenzylideneacetone) dipalladium, and the reaction may be performed at 80 to 150 ° C. for 6 to 48 hours.

Formula 11 of the present invention may be prepared by removing a protecting group from the compound represented by the following formula (13).

[Formula 13]

(T is a protecting group, and Ar ¹ and Ar ² are the same as defined in Formula 1).

The protecting group according to an embodiment of the present invention may be any functional group commonly used as a functional group recognized by those skilled in the art of organic synthesis, and as a specific example, may be a 4-methoxybenzyl group.

Formula 13 according to an embodiment of the present invention to prepare a compound 16 by reacting a compound of formula 14 and a compound of formula 15; And reacting Chemical Formula 16 with Chemical Formula 17 and Chemical Formula 18 to prepare a compound of Chemical Formula 13.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

(In Chemical Formulas 14 to 18,

T is a protecting group;

X ¹ to X ⁶ are each independently halogen;

R ²¹ to R ²⁸ independently of one another are (C 1 -C 10) alkyl;

Ar ¹ and Ar ² are the same as defined in Formula 1.)

The dibenzoazacillin compound of the present invention can produce the final compound through the Suzuki coupling reaction or the Stiletto coupling reaction, and the like, and the dibenzoazacillin compound is not limited to the above-mentioned preparation method. Of course it can be produced by.

The method for preparing the dibenzoazacillin compound according to one embodiment of the present invention is preferably carried out under an organic solvent, but of course, the reaction may also be carried out in a molten state without using a solvent. The organic solvent is not limited as long as it can completely dissolve the reactants, but specific examples thereof may be toluene, methanol, ethanol, benzene, n-heptane, tetrahydrofuran (THF), chloroform or a mixed solvent thereof. .

In another aspect, the present invention provides an organic electroluminescent device comprising a dibenzoazacillin compound according to an embodiment of the present invention. In this case, the organic electroluminescent device comprises a first electrode; Second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer may include a dibenzoazacillin compound according to an embodiment of the present invention.

Preferably the dibenzoazacillin compound according to an embodiment of the present invention may be included in the light emitting layer of the organic electroluminescent device.

Of course, the organic electroluminescent device according to an embodiment of the present invention can be manufactured by any possible method within a range that can be recognized by those skilled in the art.

The dibenzoazacillin compound represented by Chemical Formula 1 according to an embodiment of the present invention is applicable to various organic electroluminescent devices, and such organic electroluminescent devices may be a flat panel display device, a flexible display device, a monochrome or white flat lighting device. And it can be used in the device selected from the device for flexible lighting of monochrome or white, but is not limited thereto.

In general, the organic electroluminescent device according to an embodiment of the present invention will be described in detail below, but is not limited thereto.

An organic light emitting diode (OLED) manufactured according to a preferred embodiment of the present invention may include an anode, a cathode, and an organic material layer disposed therebetween.

In addition, the organic material layer of the organic light emitting device (OLED) described above may include at least one of an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. Except for including the dibenzoazacillin compound of Formula 1 in the organic layer according to an embodiment of the present invention to be prepared in a structure known in the art using conventional methods and materials in the art Of course you can.

The dibenzoazacillin compound according to an embodiment of the present invention may be included in one or more of the organic material layers, and more specifically, in the organic material layer, an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, and a hole blocking It may be used in place of one or more of the layer, the electron transport layer and the electron injection layer, or may be used to form a layer with them.

The organic electroluminescent device (OLED) according to an embodiment of the present invention is a metal or conductive on the substrate by using a physical vapor deposition (PVD) method, such as sputtering or e-beam evaporation The branch may be formed by depositing a metal oxide or an alloy thereof to form an anode, and then an organic material layer including at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer may be used as a cathode thereon. By depositing the material present. In addition, the auxiliary layer (buffer layer) may be formed between the hole transport layer and the light emitting layer or between the electron transport layer and the light emitting layer,

In addition to the above method, it can be prepared by depositing an anode material, an organic material layer, an anode material on a substrate in turn, the organic material layer is an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection It may be a multilayer structure including a layer and the like, but is not limited thereto and may have a single layer structure.

In addition, the organic layer may be prepared by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be made into a layer.

In this case, the organic electroluminescent device (OLED) may include a dibenzoazacillin compound according to an embodiment of the present invention preferably in the light emitting layer of the organic material layer, the dibenzoazacillin compound represented by Formula 1 is blue light emission As a material, it can be used as a thermally activated delayed fluorescence (TADF) dopant material.

In the organic electroluminescent device (OLED), the substrate is not only glass and quartz plates but also polyethylene terephthalate (PET), polyethylenenaphthelate (PEN), polyperopylene (PP), polyimide (PI), polycarbornate (PC), polystylene (PS), It may also be made of flexible and transparent materials such as plastics, including POM (polyoxyethlene), AS resin (acrylonitrile styrene copolymer), ABS resin (acrylonitrile butadiene styrene copolymer) and TAC (Triacetyl cellulose).

An anode is positioned on the substrate. This anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention 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 poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Etc., but is not limited thereto.

The hole injection layer is positioned on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability. The hole injection material is a material capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone or polyaniline and a polythiophene-based conductive polymer, and the like, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives the holes from the hole injection layer and transports the holes to the light emitting layer positioned thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, heat resistance of the device is required for applications for vehicle body display, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable, and materials satisfying such conditions are NPD (or NPB). ), A spiro-arylamine compound, a perylene-arylamine compound, an azacycloheptatriene compound, a bis (diphenylvinylphenyl) anthracene, a silicon germanium oxide compound, or a silicon-based arylamine compound.

The light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and preferably a material having good quantum efficiency with respect to fluorescence or phosphorescence, and more preferably the present invention. It may include a dibenzoazacillin compound represented by Formula 1 according to an embodiment of. In this case, the light emitting layer described above may implement more excellent luminous efficiency and high color purity by including the dibenzoazacillin compound of the present invention in the light emitting layer.

An electron transport layer is positioned on the light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

In addition, an electron injection layer may be stacked on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq ₃ , Be (bq) ₂ , Zn (BTZ) ₂ , Zn (phq) ₂ , PBD, spiro-PBD, TPBI, Tf-6P, or the like; aromatic compounds having an imidazole ring; boron compound; It can be produced using a low molecular weight material, such as, the electron injection layer is preferably formed in a thickness range of 100 ~ 300Å.

Finally, a cathode is positioned on the electron injection layer. The cathode serves to inject electrons, and the material used as the cathode is not limited as long as the material used for the cathode is used in the art, and a metal having a low work function is more preferable for efficient electron injection. Specific examples thereof include suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, and the like; Or their appropriate alloys; This can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

As described above, the dibenzoazacillin compound represented by Formula 1 according to an embodiment of the present invention may be used as an auxiliary layer (buffer layer) material, a hole injection material, a hole transport material, a light emitting material, an electron transport material, or an electron injection material. It may be preferably used as a hole transport material, a light emitting material (phosphorescent host) or a thermally activated delayed fluorescence dopant material, and more preferably used as a TADF dopant material.

In addition, the organic electroluminescent device including the dibenzoazacillin compound according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1 2,8-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5,10,10-triphenyl-5,10-dihydrodibenzo [b , e] [1,4] azasiline (BDTPDDA) Preparation

[Step 1] Preparation of 2,4-dibromo-N- (2,5-dibromophenyl) aniline (Compound 1)

NBS (78.89 g, 443 mmol) was added to a well-dried 2 L three-necked round bottom flask, which was dissolved in acetone (800 mL) and the temperature was lowered to 5 ^° C. Diphenylamine (15.0 g, 88.6 mmol) was divided into 10 times and added in 15 minutes. Water (50 mL) was added to form white crystals. The resulting crystals were filtered, washed with water and dried. Recrystallization with Toluene gave 30 g (70%) of the title compound as a solid.

¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.74-7.35 (s, 2H), 7.36-7.33 (d, 2H), 7.13-7.10 (d, 2H), 6.34 (s, 1H).

[Step 2] Preparation of 2,4-dibromo-N- (2,4-dibromophenyl) -N- (4-methoxybenzyl) aniline (Compound 2)

2,4-dibromo-N- (2,5-dibromophenyl) aniline (10.0 g, 20.6 mmol) was added to a well-dried 250 mL three neck round bottom flask, and NaH (1.0 g, 24.7 mmol) was added to dimethylformamide (150 mL). Put the dissolved solution. After stirring for 1 hour, 1- (chloromethyl) -4-methoxybenzene was added and stirred for another 14 hours. After completion of the reaction, a small amount of water was added to the reaction mixture, extracted with dichloromethane, the organic layer was washed with water, dried over MgSO ₄ and filtered. The solvent was removed on a rotary evaporator and then separated by column chromatography using N- Hexane / dichloromathane (4: 1) solvent to afford 9 g (56%) of the title compound as a solid.

¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.72-7.71 (s, 2H), 7.40-7.37 (d, 2H), 7.30-7.29 (d, 1H), 7.27-7.26 (d, 1H), 6.83 6.79 (d, 4H), 4.70 (s, 2H), 3.77 (s, 3H).

[Step 3] Preparation of 2,8-dibromo-5- (4-methoxybenzyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline (Compound 3)

In a well-dried 500 mL three neck round bottom flask, 2,4-dibromo-N- (2,4-dibromophenyl) -N- (4-methoxybenzyl) aniline (17.0 g, 28.1 mmol) was added and dissolved in ether (250 mL). The temperature was lowered to 0 ^o C and 2.5M n-BuLI / hexane (22.5 mL, 56.2 mmol) was added dropwise. After stirring for 30 minutes, a solution of dichlorodiphenylsilane (7.8g, 30.9 mmol) dissolved in ether (30mL) was added dropwise. Stirred at room temperature for 12 hours. Extracted with ether, the organic layer was washed with water, dried over MgSO ₄ and filtered. The solvent was removed on a rotary evaporator and then recrystallized from ethyl acetate / n-hexane (1/20) to give the title compound in a yield of 7.3 g (38%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.55-7.52 (m, 6H), 7.49-7.42 (m, 6H), 7.39-7.35 (d, 2H), 7.05-7.02 (d, 2H), 6.91 -6.88 (d, 2H), 6.85-6.82 (d, 2H), 5.1 (s, 2H), 3.81 (s, 3H).

[Step 4] 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3,5-triazine (compound 4) Manufacture

In a well-dried 100 mL three neck round bottom flask, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (1.0 g, 2.06 mmol), 4,4,4 ', 4', 5 , 5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) with KOAc and Pd (dppf) Cl ₂ And dissolved in DMF. After refluxing at 130 ^o C, the mixture was cooled to room temperature, added to cold water, stirred, and the resulting powder was filtered and washed with plenty of water.

The solid was dissolved in methylene chloride and washed with water to remove the remaining DMF as much as possible. Then, water was removed with MgSO ₄ , and Silica was applied, followed by column chromatography using N -Hexane / MC (10/1) solvent to separate the title compound as a white solid. 4 was obtained in a yield of 0.8 g (72.93%).

[Step 5] 2,8-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5- (4-methoxybenzyl) -10,10-diphenyl-5, Preparation of 10-dihydrodibenzo [b, e] [1,4] azasiline (Compound 5)

2,8-dibromo-5- (4-methoxybenzyl) -10,10-diphenyl-5,10dihydrodibenzo [b, e] [1,4] azasiline (Compound 3, 7.0 g) in a well-dried 250 mL three-neck round bottom flask , 11.1 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetra methyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3,5-triazine (Compound 4, 12.14 g, 27.9 mmol) was added and dissolved with toluene (150 mL). K ₂ CO ₃ (2M) and tetrakis (triphenylphosphine) palladium (0) Pd (PPh ₃ ) ₄ (0.52 g, 0.45 mmol) were added thereto, adjusted to 100 ^o C, and stirred for 24 hours. Extracted with ethyl acetate, washed organic layer with water, dried over MgSO ₄ , coated with Silica and separated by column chromatography using N -Hexane / dichloromathane (1/1) solvent to obtain 7 g (58) of the title compound 5 as a solid. %).

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ) δ = 8.84-8.81 (d, 12H), 7.98-7.97 (d, 2H), 7.80-7.73 (m, 10H), 7.68-7.61 (m, 12H) 7.54 -7.47 (m, 6H), 7.28-7.24 (d, 4H), 6.94-6.91 (d, 2H), 5.37 (s, 2H), 3.85 (s, 3H).

[Step 6] 2,8-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] Preparation of [1,4] azasiline (Compound 6)

2,8-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5- (4-methoxybenzyl) -10, in a well-dried 250 mL three neck round bottom flask 10-diphenyl5,10-dihydro-dibenzo [b, e] [1,4] azasiline (7.00 g, 6.45 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (3.37 g, 14.8 mol) was dissolved in toluene (70 mL) and H ₂ O (7 mL), and the mixture was stirred at 80 ^° C. for 14 hours. The solution was extracted with ethyl acetate, washed well with water, dried with MgSO ₄ and separated by column chromatography using N- Hexane / ethyl acetate (5/1) solvent to obtain 3.4 g (55%) of the title compound as a solid. Obtained at.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ) δ = 8.95-8.94 (s, 1H), 8.68-8.66 (d, 5H), 7.71-7.33 (m, 19H), 7.30-7.08 (m, 14H) , 6.90-6.83 (m, 5 H), 6.47 (s, 1 H).

[Step 7] 2,8-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -5,10,10-triphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline (BDTPDDA) Preparation

In a well-dried 100 mL three neck round bottom flask, 2,8-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10dihydrodibenzo [ b, e] [1,4] -azasiline (3.00 g, 3.11 mmol), iodo-benzene (1.47 g, 9.33 mmol), sodium-t-butoxide (0.60 g, 6.22 mmol), tris (t-butyl) phosphine (0.06 g, 0.31 mmol) and Tris (dibenzylideneacetone) dipalladium (0) (0.14 g, 0.15 mmol) were added and dissolved in toluene (30 mL). The temperature was adjusted to 110 ° C. and heated to reflux for 12 hours. After the temperature was lowered to room temperature, the mixture was extracted with chloroform, the organic layer was washed with water, dried over MgSO _4, and the solvent was removed using a rotary evaporator. Column chromatography using n-Hexane / dichloromethane (1/1) solvent to give the title compound as a solid yield of 2.3 g (71%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ = 8.82-8.78 (d, 12H), 8.02-8.01 (d, 2H), 7.81-7.76 (m, 4H), 7.73-7.71 (d, 6H), 7.66 -7.57 (m, 15H), 7.51-7.46 (m, 6H), 7.43-7.41 (d, 2H), 6.62-6.59 (d, 2H). MS (EI) m / z 1039.38 (M < + >).

[Comparative Example 1] 2,7-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10-phenyl-10H-spiro [acridine-9,9'- fluorene] (BDTPSAF)

[Step 1] Preparation of 2,7-dibromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene]

10-phenyl-10H-spiro [acridine-9,9'-fluorene] (2.3 g, 5.64 mmol) was dissolved in 100 mL of chloroform under a nitrogen atmosphere, and the temperature was lowered to 0 ° C., followed by N-bromosuccinimide ( NBS) (4.01 g, 22.57 mmol) was added slowly. The reaction mixture was stirred at 0 ° C. for 2 hours and then at room temperature for 24 hours. After the reaction was completed, the solvent of the reaction mixture was removed, and then the obtained solid was dissolved in dichloromethane and extracted by adding water. The obtained filtrate was removed with residual water with MgSO ₄ and purified by column chromatography (ethyl acetate / n-hexane (1/10)) to obtain 1.5 g (47%) of the title compound as white.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ) δ = 7.84 (d, J = 7.5 Hz, 2H), 7.74 (t, J = 7.5 Hz, 2H), 7.65-7.59 (m, 1H), 7.49- 7.40 (m, 6H), 7.32 (d, J = 7.2 Hz, 2H), 7.02 (d, J = 9 Hz, 2H), 6.47 (d, J = 2.1 Hz, 2H), 6.24 (d, J = 9 Hz, 2H). MS EI (m / z): 562.98 (M < + >, 100%).

[Step 2] 2,7-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10-phenyl-10H-spiro [acridine-9,9'-fluorene ] (BDTPSAF).

2,7-Dibromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene] (2.0 g, 3.53 mmol), 2,4-diphenyl-6- (4- (4,4, 50 mL of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3,5-triazine (3.39 g, 7.78 mmol) and Pd (PPh ₃ ) ₄ (0.24 g) Toluene was added and 2M K ₂ CO ₃ (5.3 mL) was added thereto and stirred at 100 ° C. for 24 hours. After addition of a small amount of water and methanol, the solid obtained by filtration was purified by column chromatography (ethyl acetate / n-hexane (1/10)) to obtain 0.8 g (73%) of the title compound as a white solid.

¹ H-NMR (300 MHz, CDCl ₃ ): δ = 8.78-8.75 (m, 8H), 8.69-8.67 (m, 4H) 7.90 (d, J = 7.8 Hz, 2H), 7.82 (t, J = 7.8 Hz, 2H), 7.64-7.55 (m, 18H), 7.50-7.34 (m, 10H), 6.85 (d, J = 2.1 Hz, 2H), 6.57 (d, J = 8.4 Hz, 2H). 13 C-NMR (500 MHz, CDCl 3): δ = 171.51, 156.09, 144.37, 141.20, 140.73, 139.34, 136.33, 134.21,

132.41, 131.29, 130.94, 128.93, 128.59, 126.48, 126.27, 125.71, 120.26, 115.39, 57.05. MS MALDI (m / z): 1022.39 (M < + >, 100%). Element Anal. Calcd: C, 85.77; H, 4.63; N, 9.59; Found: C, 85.82; H, 4.45; N, 9.39;

[Comparative Example 2] 5- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1 , 4] Manufacture of azasiline (DTPDDA)

[Step 1] Preparation of 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline (Compound 10)

[Step 1] and [2] of Example 1, except that bis (2-bromophenyl) amine was used instead of 2,4-dibromo-N- (2,5-dibromophenyl) benzenamine in [Step 1] of Example 1. Compound 9 was prepared in the same manner as in Step] and used in a subsequent reaction.

In a well-dried 150 mL three-neck round bottom flask, 5- (4-methoxybenzyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline (37 g, 78.8 mmol) and DDQ ( 19.67 g, 86.6 mmol), 370 mL of Toluene and 37 mL of H 2 O were added to a round flask and stirred at 80 ° C. for 14 hours. After completion of the reaction, the solvent was removed, and then extracted three times using ethyl acetate. The extracted organic layer was dried using MgSO _4, and then the solvent was removed using a rotary evaporator, and separated by column chromatography using a hexane / ethyl acetate (7/1) solvent to obtain compound 10, 7.5 g (yield = 27). %) Obtained.

¹ H-NMR (300 MHz, D2O / DMSO) [ppm] δ = 9.43 (s, 1H), 7.48-7.32 (m, 14H), 7.10-7.07 (m, 2H), 6.90-6.85 (m, 2H) .

[Step 2] 5- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1, 4] Manufacture of azasiline (DPTDDDA)

In a well-dried 30 mL round bottom flask, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (0.5 g, 1.29 mmol), 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline (0.41 g, 1.16 mmol), Na-t-butxide (0.19 g, 1.93 mmol), tris (tertbutyl) phosphine (0.03 g, 0.13 mmol) and Pd ₂ (dba) ₃ (0.06 g, 8.1 mmol) was dissolved in 5 ml of toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, water was poured and extracted three times using chloroform. The extracted organic layer was dried using MgSO ₄ , the solvent was removed using a rotary evaporator, and separated by column chromatography using a MC / n-Hexane (2/1) solvent to obtain a compound DPTDDA, 0.54 g (yield = 63%).

¹ H-NMR (300 MHz, CDCl ₃ ) [ppm] δ = 9.05-9.02 (d, 2H), 8.85-8.82 (d, 4H), 7.69-7.59 (m, 12H), 7.54-7.52 (d, 2H ), 7.45-7.38 (m, 6H), 7.24-7.18 (t, 2H), 7.01-6.97 (t, 2H), 6.58-6.55 (d, 2H); ¹³ C-NMR (500 MHz, CDCl 3, δ): 171.88, 171.10, 149.70, 147.71, 136.11, 136.02, 135.82, 135.23, 132.69,131.68, 131.29, 130.41, 129.63, 129.03, 128.73, 127.94, 120.31, 117.52. ; Mass: C 45 H 32 N 4 Si calcd. 656.24; found. 656.24

(Example 2) Measurement of optical properties of the compound obtained in Example 1 and Comparative Examples 1 and 2

In order to evaluate the UV absorption spectrum and the PL (photoluminescence) spectrum of each compound prepared in Example 1 and Comparative Examples 1 and 2, each of the compounds of Example 1 and Comparative Example 1 in a concentration of 0.2 mM in toluene After dilution, the UV absorption spectrum was measured using a Shimadzu UV-350 Spectrometer, and each of the compounds of Examples 1 and Comparative Examples 1 and 2 was diluted in toluene at a concentration of 10 mM and xenon. Photoluminecscence (PL) spectra were measured using an ISC PC1 Spectrofluorometer equipped with a (Xenon) lamp, and the results are shown in Table 1 below.

compound UV-Vis Sol (nm) PL Sol (nm) Example 1 BDTPDDA 401 459 Comparative Example 1 BDTPSAF 361 469 Comparative Example 2 DTPDDA 375 460

As shown in Table 1, it can be seen that the compounds of Examples 1 and Comparative Examples 1 and 2 of the present invention can be used as blue light emitting materials because the PL spectrum emits light at around 460 nm.

Example 3 Fabrication of Organic Electroluminescent Device Using Compound Obtained in Example 1

The transparent electrode ITO thin film cell obtained from the glass for OLED was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water sequentially, and then stored in isopropanol and used.

The device was composed of Glass / indiumtin oxide (ITO) (75 nm) / 6wt% ReO ₃ : mCP (45 nm) / mCP (15 nm) / mCP: 10wt% Example 1 (compound of the present invention) (15 nm) / TSPO1 (15 nm) / 6wt% Rb ₂ CO ₃ : TSPO1 (35 nm) / Al (100 nm).

6% ReO ₃ : mCP was deposited on the ITO thin film to form a 45 nm hole injection layer, and then 1,3-Bis (N-carbazolyl) benzene (mCP) was deposited to form a 15 nm hole transport layer. 9- (3- (9H-carbazol-9-yl) phenyl) -3- (diphenylphosphoryl) -9H-carbazole (mCP) was used as the host material, and Example 1 (blue light emitting material, the compound of the present invention) was used. The light emitting layer was used as a dopant of the light emitting layer, and the concentration of the co-host and the dopant was 10 wt% (mCP: TSPO1: Example 1 (compound of the present invention)) to form a light emitting layer by vacuum deposition at 15 nm. 15 nm of diphenyl (4- (triphenylsilyl) phenyl) phosphine oxide (TSPO1) was deposited as an electron transport layer, and 6wt% Rb ₂ CO ₃ : TSPO1 was deposited to 50 nm as an electron injection layer, and the electron injection and electron transport layer was deposited. An organic electroluminescent device was manufactured by depositing Al to form a cathode.

(Comparative Examples 3 to 4) Fabrication of Organic Electroluminescent Device Using Compounds Obtained in Comparative Examples 1 and 2

An organic electroluminescent device was manufactured in the same manner as in Example 3, except that the compound of Comparative Example 1 and Comparative Example 2 was used instead of the dibenzoazocillin compound of the present invention.

Table 2 shows EQEs and color coordinates according to current densities of organic electroluminescent devices prepared in Example 3 and Comparative Examples 3 to 4 of the present invention. As shown in Table 2, the organic electroluminescent device of Example 2 employing the dibenzoazocillin compound of Example 1 of the present invention was superior to the organic electroluminescent devices employing the compounds of Comparative Example 1 and Comparative Example 2. You can see that it represents EQE.

In addition, Table 2 and Figure 1 shows the color coordinates of the organic EL device manufactured in Example 2, Comparative Example 3 and Comparative Example 4 of the present invention.

compound EQE (%) ^a Turn-on (volts) CIE (xy) ^b Example 3 BDTPSAF 8.5 3.5 (0.142, 0.116) Comparative Example 1 BDTPSAF 8.5 3.8 (0.139, 0.189) Comparative Example 2 DTPDDDA 8 5.7 (0.149, 0.197)

a: CIE 1931 coordinates at 500 cd / m ² .b: External quantum efficiency of maximum

As shown in Table 2 and Figure 1 of Comparative Example 3 and Comparative Example 4 in which the organic electroluminescent device employing the dibenzoazocillin compound of Example 1 of the present invention employs the compounds of Comparative Example 1 and Comparative Example 2 It can be seen that the organic electroluminescent device has more excellent color purity and shows deep blue color of high purity.

From this, it can be seen that the dibenzoazocillin compound according to an embodiment of the present invention has better color purity without lowering efficiency, and thus the organic electroluminescent device employing the dibenzoazocillin compound exhibits improved blue light emission. The improved color purity that the azocillin compound has in comparison to the compound of the comparative example corresponds to significant effects that cannot be easily reached by those skilled in the art.

Claims (8)

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

(In Formula 1,
R ¹ is phenyl;
Ar ¹ and Ar ² are each independently phenylene unsubstituted or substituted with (C1-C30) alkyl.) delete The method of claim 1,
In Formula 1, Ar ¹ and Ar ² are the same as each other (C1-C30) alkyl substituted or unsubstituted phenylene dibenzoazacillin compound. delete The method of claim 1,
The dibenzoazacillin compound is selected from the following compounds.

A method for preparing a dibenzoazacillin compound represented by the following Chemical Formula 1, comprising the step of reacting the following Chemical Formula 12 with Chemical Formula 11 in the presence of a catalyst.
[Formula 1]

[Formula 11]

[Formula 12]

(In Formula 1, Formula 11 and Formula 12,
R ¹ is phenyl;
Ar ¹ and Ar ² are independently of each other phenylene unsubstituted or substituted with (C1-C30) alkyl;
X is halogen.) An organic electroluminescent device comprising the dibenzoazacillin compound of any one of claims 1, 3 and 5. The method of claim 7, wherein
The dibenzoazacillin compound is an organic electroluminescent device that is included in the light emitting layer of the organic electroluminescent device.

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