KR20110123172A - Triphenylene-based compounds that substitute aryl amine compounds and organic electroluminescent device comprising same - Google Patents

Abstract

PURPOSE: A triphenylene compound is provided to improve power efficiency and luminous efficiency when using as the material for an organic electroluminescent display by high hole injection ability and hole transmission ability relative to NPB which is used as the material for hole injection and transmission. CONSTITUTION: A triphenylene compound is in the chemical formula 1. In the chemical formula 1: A is a single bond, phenyl, naphthyl, and substituted or non-substituted heteroaryl with a 6-10 nucleus atom number; B is the substituted or non-substituted C6-C10 aryl and substituted or non-substituted heteroaryl with a 6-10 nucleus atom number; X is one selected from N, O and S; each l and m is independently 0 or 1; n is integer 1 or 2; and Ar1-Ar4 are substituted or non-substituted C6-C20 aryl, substituted or non-substituted heteroaryl with a 6-10 nucleus atom number. When X is O or S, one among l and m is 0.

Description

Triphenylene compound containing an aromatic amine, and an organic electroluminescent device comprising the same.

The present invention includes a novel triphenylene compound having excellent electron transport ability, hole injection and / or transport ability, and / or luminous ability, and the triphenylene compound in at least one organic layer, thereby providing luminous efficiency, brightness, thermal stability, driving voltage, The present invention relates to an organic electroluminescent device having improved characteristics such as lifetime.

In general, organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. That is, when the organic layer is positioned between the anode and the cathode, a voltage is applied between the two electrodes, and holes are injected into the organic layer and electrons are injected into the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground, they shine.

The study of organic electroluminescent (EL) devices (hereinafter simply referred to as 'organic EL devices') led to the blue electroluminescence using anthracene single crystals in 1965, based on Bernanose's observation of organic thin film emission. By (Tang), an organic EL device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer has been proposed. Since then, in order to make high-efficiency, high-life organic EL devices, the development has been made in the form of introducing each characteristic organic material layer in the device, leading to the development of specialized materials used therein.

Such organic EL devices include an indium tin oxide (ITO) substrate, an anode, a hole injection layer that selectively receives holes from an anode, a hole transport layer that selectively transfers holes, a light emitting layer where holes and electrons recombine to emit light, and optionally an electron It consists of an electron transporting layer for transferring the electrons, optionally an electron injection layer for receiving electrons from the cathode and the cathode. The reason why the organic EL device is manufactured in a multi-layer as described above is that the movement speeds of the holes and the electrons are different. If the appropriate hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer are made, the holes and the electrons can be effectively transferred. In addition, the hole and the electrons in the device are balanced to improve the luminous efficiency. Electrons injected from the electron injection layer and holes transferred from the hole injection layer recombine in the emission layer to form excitons, and fall from the singlet excited state to the ground state and are called fluorescence, and fall from the triplet excited state to the ground state. Luminescence is called phosphorescence. Theoretically, when the exciton is generated when the carrier is recombined in the emission layer, the ratio of singlet and triplet excitons is generated at a ratio of 1: 3, and when phosphorescence is used, the internal quantum efficiency may be 100%.

In general, a carbazole compound such as CBP (4,4-dicarbazolybiphenyl) is used as the phosphorescent host material, and a metal complex compound containing heavy atoms such as Ir and Pt is used as the phosphorescent dopant material. This is widely used. However, CBP, which is currently used phosphorescent host material, has a low glass transition temperature (T _g ) of about 110 ° C., and crystallization in the device is easy, resulting in a very short lifetime of an organic EL device of about 150 hours.

An object of the present invention is to include a triphenylene-based compound having excellent electron transporting ability, hole injection and / or transporting ability and / or light emitting ability (fluorescence or phosphorescence) in at least one organic layer, thereby providing luminous efficiency, brightness, thermal stability, driving It is to provide an organic EL device having improved characteristics such as voltage and lifetime.

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

Wherein A is a single bond, phenyl, naphthyl, substituted or unsubstituted heteroaryl having 6 to 10 nuclear atoms, wherein the substituent introduced into the hetero aryl is a halogen atom, an alkyl group having 1 to 3 carbon atoms, and 6 carbon atoms To 10 aryl groups;

B is substituted or unsubstituted aryl between C6 and C10, substituted or unsubstituted heteroaryl having 6 to 10 nuclear atoms, wherein the substituent introduced into the aryl or heteroaryl is a halogen atom, an alkyl group having 1 to 3 carbon atoms And an aryl group having 6 to 10 carbon atoms;

In this case, A and B may be the same as or different from each other independently,

X is one of N, O, S,

l, m are each independently 0 or 1, where X is O or S, then one of l and m is 0,

n is an integer of 1 or 2,

Ar ₁ to Ar ₄ is substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted heteroaryl having 5 to 20 nuclear atoms, wherein the substituents introduced into aryl, heteroaryl are deuterium or halogen atoms, carbon atoms 1 It is selected from the group consisting of an alkyl group of ˜3, an aryl group having 6 to 10 carbon atoms, each may be the same or different independently.

Here, Ar ₁ and Ar ₂ may be bonded to adjacent substituents and / or A to each other to form a condensed ring, and Ar ₃ and Ar ₄ may be bonded to adjacent substituents and / or B to each other to form a condensed ring. have.

In this case, the condensed ring refers to forming a ring by combining a substituent with a substituent.

The atom included in the hetero aryl may be a nitrogen atom, but is not limited thereto.

In addition, the present invention, the anode; cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes the compound of Formula 1 described above.

The compound of Chemical Formula 1 according to the present invention is used as the material for the organic EL device can exhibit the power efficiency and luminous efficiency improvement through a high hole injection and transport ability compared to the conventional NPB used as a hole injection and transport material Can be.

In addition, compared to 4,4-dicarbazolybiphenyl (CBP), which was used as a phosphorescent host material, low power, high efficiency, high brightness, and improved durability and lifetime can be obtained.

In the present invention, the triphenylene compound having a wide singlet energy level and a high triplet energy level has an effect on the aryl amine substituent which is an electron donating group (EDG) and the singlet and triplet energy levels of the compound. It is characterized by the introduction of less influent linkers (A, B).

That is, in the existing triphenylene compound having a wide singlet energy level and a high triplet energy level, the singlet energy is regulated by introducing a functional group such as aryl amine, and the phenyl or naphthyl, having 6 to 10 nuclear atoms. By introducing functional groups with similar energy levels through meta bonds to small molecular weight aromatic linkers such as heteroaryls (rings), controlled singlet and triplet energy levels can be maintained.

At this time, when the functional group is substituted at the para or ortho position in the aromatic linkage, the conjugation effect and the pi electron exchange effect directly affect the singlet and triplet energy of the molecule, but minimize them through meta-bonding. can do.

The above-described substituents and linkers can be effectively used as a hole injection layer and hole transport layer material of an organic EL device by effectively adjusting the energy level of triphenylene, maximizing the hole blocking ability and the hole injection / transport ability. In addition, when used as a light emitting layer material of the phosphorescent organic EL device through the conversion of the linking group, it is possible to provide a compound exhibiting improved light emission characteristics.

In addition, by increasing the molecular weight by introducing the linking groups represented by A and B, durability and lifespan improvement can be exhibited by improving the glass phase transition temperature (T _g ).

Furthermore, when the linker A or B to be introduced is replaced with a meta-position, the triplet energy level of the triphenylene compound is maintained, thereby exhibiting improved efficiency even as a light emitting layer material for a phosphorescent organic EL device. Can be. Accordingly, the fluorescent or phosphorescent organic EL device including the compound of the present invention can provide a full color display panel and the like which are greatly improved in light emission performance and lifetime.

Compounds represented by the general formula (1) of the present invention, may be represented by more specifically to the following formulas (2) to (4).

In Chemical Formulas 2 to 4,

A, B, Ar ₁ to Ar ₄ and n are the same as defined in Chemical Formula 1.

In this case, when A or B is a hetero aryl having 6 to 10 nuclear atoms, it may be selected from a substituent group consisting of the following Chemical Formula 5.

In the above formula, a plurality of Z introduced into the substituent group of the formula (5) are each independently and may be the same or different from each other, even if they are the same, at least one of the plurality of Z is a nitrogen atom, the remainder is a carbon atom.

In addition, in Chemical Formula 1, Ar ₁ and Ar ₂ may be bonded to adjacent substituents and / or A to form a condensed ring, and Ar ₃ and Ar ₄ may be bonded to adjacent substituents and / or B to be condensed. Can be formed.

The following formulas are representative examples of the compound represented by Formula 1 of the present invention, but the compound represented by Formula 1 of the present invention is not limited to those illustrated below.

The compound represented by general formula (I) of the present invention can be synthesized according to the general synthetic method (Chem Rev, 60: 313 ( 1960); J. Chem SOC 4482 (1955); Chem Rev. 95:..... 2457 (1995)). Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.

Another aspect of the present invention relates to an organic electroluminescent device comprising the compound represented by Formula 1 according to the present invention.

Specifically, the present invention is an anode (anode); Cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer includes a compound represented by Chemical Formula 1.

The compound of Formula 1 may be included alone or in plurality.

The organic layer including the compound represented by Formula 1 of the present invention may be any one or more of a hole injection layer, a hole transport layer, an electron transport layer and a light emitting layer. Preferably, the compound represented by Formula 1 may be included in the organic EL device as a hole injection layer and a hole transport layer material, in which case the organic EL device may maximize the hole blocking ability and the hole injection / transport ability. In addition, the compound represented by Chemical Formula 1 may be used as a light emitting layer material of the organic EL device, thereby providing improved efficiency.

In the present invention, the light emitting layer may include a phosphorescent dopant material or a fluorescent dopant material. Preferably, the compound represented by Formula 1 of the present invention may be included in the organic EL device as a blue, green, and / or red phosphorescent host, a fluorescent host, a hole transport material, a hole injection material, and / or an electron transport material. .

In addition, the compound represented by Formula 1 according to the present invention has a high glass transition temperature of 150 ℃ or more. Therefore, when the compound is used as the organic layer of the organic EL device, since the crystallization is minimized in the organic EL device, the driving voltage of the device can be lowered, and the luminous efficiency, luminance, thermal stability, and lifetime characteristics can be improved.

As a non-limiting example of the organic EL device structure according to the present invention, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode may be sequentially stacked. In this case, at least one of the light emitting layer, the hole injection layer, the hole transport layer, and the electron transport layer may include a compound represented by Chemical Formula 1. An electron injection layer may be positioned on the electron transport layer.

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

In the organic EL device of the present invention, the organic layer including the compound of Formula 1 may be formed by vacuum deposition or solution coating. Examples of the solution application include spin coating, dip coating, doctor blading, inkjet printing or thermal transfer method, but is not limited thereto.

The organic EL device of the present invention forms an organic layer and an electrode using materials and methods known in the art, except that at least one layer of the organic layer in the device includes the compound represented by Formula 1 of the present invention. Can be prepared.

For example, a silicon wafer, quartz, glass plate, metal plate, plastic film or sheet may be used as the substrate.

The anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals 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 and polyaniline; Or carbon black, but is not limited thereto.

Cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

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

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

Preparation Example 1 Synthesis of triphenylene-2,7-diyl bis (trifluoromethanesulfonate)

< Step 1> Synthesis of Compound 1 (3,3'-dimethoxy-o-terphenyl)

Scheme 1

1,2-dibromobenzene (50g, 214 mmol), 3-methoxyphenylboronic acid (65.1g, 428 mmol) and Pd (PPh ₃ ) ₄ (4.95g, 4.28 mmol) were added to the flask and dissolved in 1.4 L of toluene under nitrogen atmosphere. Then, 1.2 L of an aqueous solution of sodium carbonate (118.2 g, 856 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours. After the reaction was completed, the mixture was extracted three times with 200 ml of dichloromethane, and the extract was dried with excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 4: 1 (v: v)] to give compound 15 (43.5 g, yield 70%) as a white solid.

GC-Mass (Theoretical value: 290.13 g / mol, Measured value: 290 g / mol)

<Step 2> Synthesis of Compound 2 (2,7-dimethoxytriphenylene)

Scheme 2

Compound 1 (40 g, 137 mmol) obtained in <Step 1> was placed in a flask and dissolved in 1 L of dichloromethane under a nitrogen atmosphere. Then, Iron (III) chloride (44.4 g, 274 mmol) was added thereto, and the mixture was stirred at room temperature for 12 hours. Stirred. After adding 2 equivalents of iron (III) choloride, the mixture was further stirred for 1 hour, and 1 liter of methyl alcohol and water were added at a ratio of 1: 1. After the reaction was completed, the organic layer was separated, dried over excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was separated by silica gel column chromatography [n-Hexane: Dichloromethane = 2: 3 (v: v)] to give 31.6 g of product which was recrystallized in 600 ml of acetonitrile to give a pale yellow solid Compound 2 (28 g, yield). 70%) was obtained.

GC-Mass (Theoretical value: 288.12 g / mol, Measured value: 288 g / mol),

Step 3 Synthesis of Compound 3 (2,7-dihydroxytriphenylene)

Scheme 3

Compound 2 (25 g, 86 mmol) and pyridine hydrochloride (100 g, 86 mmol) obtained in <Step 2> were placed in a flask and stirred at reflux for 90 minutes at 220 ° C. under a nitrogen atmosphere. After the reaction was completed, the crude product was washed with excess water to give compound 3 (20 g, yield 88%).

GC-Mass (Theoretical value: 260.08 g / mol, Measured value: 260 g / mol),

Step 4 Synthesis of Compound 4 (triphenylene-2,7-diyl bis (trifluoromethanesulfonate))

Scheme 4

Compound 3 (20 g, 77 mmol) obtained in <Step 3> was placed in a flask, dissolved in 385 ml of pyridine under a nitrogen atmosphere, and stirred at 0 ° C. Trifluoromethanesylfonyl anhydride (43.5 g, 154 mmol) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the reaction product was concentrated under reduced pressure, and the obtained solid was placed in a flask. 500 ml of methyl alcohol was added thereto, and the mixture was stirred and filtered for 1 hour to obtain 35 g of a mixture of white solid. The crude product was recrystallized from hexane / dichloromethane to give compound 4 (28 g, yield: 68%) as a white solid.

GC-Mass (Theoretical value: 523.98 g / mol, Measured value: 524 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 7.72 to 7.75 (m, 2H), 7.78 to 7.80 (m, 2H), 8.77 to 8.79 (m, 4H), 8.92 to 8.94 (m, 2H )

[ Synthetic example  1]: compound Inv  1, manufacture

Compound Inv 1 was synthesized through the reaction route of Scheme 5 below.

Scheme 5

1) Step 1: Synthesis of Intermediate 5

Compound 4 (10 g, 19 mmol) obtained in the <Preparation Example 1>, N- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -N -phenylbenzenamine (6.34 g, 17.1 mmol) and Pd (PPh ₃ ) ₄ (0.65 g, 0.57 mmol) were placed in a flask and dissolved in 100 mL of toluene under a nitrogen atmosphere, followed by potassium carbonate (5.25 g, 38 mmol). 20 mL of an aqueous solution was added thereto, and the mixture was stirred under reflux for 12 hours. After completion of the reaction by adding 50 ml of water, the mixture was extracted three times with 30 ml of dichloromethane, the extract was dried over excess magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 7: 3 (v: v)] to give compound 5 (8.2 g, yield 70%) as a white solid.

GC-Mass (Theoretical value: 619.14 g / mol, Measured value: 619 g / mol)

2) Step 2: Synthesis of Inv 1

Compound 5 (8 g, 12 mmol), diphenylamine (2.6 g, 15 mmol) and Pd (OAc) ₂ (0.08 g, 0.36 mmol) obtained in <Step 1>, BINAP (0.45 g, 0.72 mmol) and potassium Carbonate (3.31 g, 24 mmol) was added to the flask and dissolved in 80 mL of toluene under a nitrogen atmosphere, followed by stirring under reflux for 12 hours. After the reaction was completed, 50 ml of water was added, followed by extraction three times with 30 ml of dichloromethane, and the extract was dried over excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 3: 1 (v: v)] to give the compound Inv 1 (5.2 g, yield 68%) as a white solid.

GC-Mass (Theoretical value: 638.27 g / mol, Measured value: 638 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 6.46 to 6.52 (m, 10H), 6.98 to 7.08 (m, 13H), 7.32 (s, 1H), 7.46 (m, 2H), 7.82 to 7.88 (m, 2H), 8.12 to 8.18 (m, 2H), 8.68 (m, 1H), 8.93 (m, 1H), 9.15 (s, 1H)

Synthesis Example 2 Preparation of Compound Inv 3

Compound Inv 3 was synthesized through the reaction route of Scheme 6 below.

Scheme 6

1) Step 1: Synthesis of Intermediate 6

Compound 4 (10 g, 19 mmol) obtained in the <Preparation Example 1>, N- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -N Aqueous solution of -phenylbenzenamine (6.34 g, 17.1 mmol) and Pd (PPh ₃ ) ₄ (0.65 g, 0.57 mmol) in a flask, dissolved in 100 mL of toluene under nitrogen atmosphere, and dissolved with potassium carbonate (5.25 g, 38 mmol) 20 mL was added and stirred at reflux for 12 h. After completion of the reaction by adding 50 ml of water, the mixture was extracted three times with 30 ml of dichloromethane, the extract was dried over excess magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 7: 3 (v: v)] to give compound 6 (8.6 g, yield 73%) as a white solid.

GC-Mass (Theoretical value: 619.14 g / mol, Measured value: 619 g / mol)

2) Step 2: Synthesis of Inv 3

Compound 5 (8 g, 12 mmol), diphenyl amine (2.6 g, 15 mmol) and Pd (OAc) ₂ (0.08 g, 0.36 mmol) obtained in <Step 1>, BINAP (0.45 g, 0.72 mmol) and potassium Carbonate (3.31 g, 24 mmol) was added to the flask and dissolved in 80 mL of toluene under a nitrogen atmosphere, followed by stirring under reflux for 12 hours. After the reaction was completed, 50 ml of water was added, followed by extraction three times with 30 ml of dichloromethane, and the extract was dried over excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 3: 1 (v: v)] to give the compound Inv 3 (5.5 g, 72% yield) as a white solid.

GC-Mass (Theoretical value: 638.27 g / mol, Measured value: 638 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 6.42 to 6.46 (m, 9H), 6.68 (m, 1H), 6.84 (s, 1H), 6.98 to 7.08 (m, 14H), 7.32 ( s, 1H), 7.82 to 7.88 (m, 2H), 8.12 to 8.18 (m, 2H), 8.68 (m, 1H), 8.93 (m, 1H), 9.15 (s, 1H)

Synthesis Example 3 Preparation of Compound Inv 6

Compound Inv 6 was synthesized through the reaction path of Scheme 7 below.

Scheme 7

1) Step 1: Synthesis of Intermediate 7

Compound 4 (10 g, 19 mmol) obtained in the <Preparation Example 1>, N- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -N -bis (diphenyl) benzenamine (8.9 g, 17.1 mmol) and Pd (PPh ₃ ) ₄ (0.65 g, 0.57 mmol) were placed in a flask, dissolved in 100 mL of toluene under nitrogen atmosphere, and then potassium carbonate (5.25 g, 38 mmol) 20 mL of an aqueous solution was added thereto, and the mixture was stirred under reflux for 12 hours. After completion of the reaction by adding 50 ml of water, the mixture was extracted three times with 30 ml of dichloromethane, the extract was dried over excess magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 7: 3 (v: v)] to give compound 7 (8.2 g, yield 56%) as a white solid.

GC-Mass (Theoretical value: 771.21 g / mol, Measured value: 771 g / mol)

2) Step 2: Synthesis of Inv 6

Compound 6 (6.1 g, 8 mmol), Bis (diphenyl) amine (3.1 g, 9.6 mmol) and Pd (OAc) ₂ (0.05 g, 0.24 mmol) obtained in <Step 1>, BINAP (0.3 g, 0.48 mmol) And potassium carbonate (3.31 g, 24 mmol) were added to a flask, dissolved in 60 mL of toluene under a nitrogen atmosphere, and stirred under reflux for 12 hours. After the reaction was completed, 30 ml of water was added, followed by extraction three times with 20 ml of dichloromethane, and the extract was dried over excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 3: 1 (v: v)] to give compound Inv 6 (4.9 g, yield 65%) as a white solid.

GC-Mass (Theoretical value: 942.40 g / mol, Measured value: 942 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 6.52 (m, 10H), 7.08 (m, 1H), 7.32 (s, 1H), 7.46 ~ 7.48 (m, 22H), 7.75 (m, 8H), 7.82 to 7.88 (m, 2H), 8.12 to 8.18 (m, 2H), 8.68 (m, 1H), 8.93 (m, 1H), 9.15 (s, 1H)

Synthesis Example 4 Preparation of Compound Inv 30

Compound Inv 30 was synthesized through the reaction path of Scheme 8 below.

Scheme 8

1) Step 1: Synthesis of Inv 30

Compound 4 (10 g, 19 mmol) obtained in the <Preparation Example 1>, N- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -N -phenylbenzenamine (15.5 g, 41.8 mmol) and Pd (PPh ₃ ) ₄ (0.65 g, 0.57 mmol) were placed in a flask, dissolved in 100 mL of toluene under nitrogen atmosphere, and then dissolved in sodium carbonate (6 g, 57 mmol) in an aqueous solution 20 mL was added and stirred at reflux for 12 h. After completion of the reaction by adding 50 ml of water, the mixture was extracted three times with 50 ml of dichloromethane, the extract was dried over excess magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 4: 1 (v: v)] to give compound 7 (11.12 g, yield 82%) as a white solid.

GC-Mass (Theoretical value: 714.30 g / mol, Measured value: 714 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 6.46 (m, 8H), 6.68 (m, 2H), 6.84 (m, 2H), 6.98 to 7.07 (m, 14H), 7.85 (m, 2H), 8.07 (m, 2H), 8.52-8.58 (m, 4H), 8.74 (m, 2H)

Synthesis Example 5 Preparation of Compound Inv 33

Compound Inv 33 was synthesized through the reaction path of Scheme 9 below.

Scheme 9

1) Step 1: Synthesis of Intermediate 8

1,3,5-Tribromobenzene (37 g, 120 mmol), diphenylamine (18.3 g, 108 mmol) and Pd (OAc) ₂ (0.8 g, 3.6 mmol), BINAP (4.47 g, 7.2 mmol), Potassium carbonate (33.2 g, 240 mmol) was added to the flask and dissolved in 1 L of toluene under a nitrogen atmosphere, followed by stirring under reflux for 12 hours. After 12 hours, 500 ml of water was added to terminate the reaction. After extraction three times with 300 ml of dichloromethane, the extract was dried over an excess of magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 4: 1 (v: v)] to give compound 8 (36.7 g, yield 65%) as a white solid.

GC-Mass (Theoretical value: 490.10 g / mol, Measured value: 490 g / mol)

2) Step 2: Synthesis of Intermediate 9

Compound 8 (24.5 g, 50 mmol), Bis (pinacolate) diboron (25.4 g, 100 mmol) and Pd (dppf) ₂ Cl ₂ (1.7 g, 1.5 mmol) obtained in <Step 1>, potassium acetate (14.5 g , 150 mmol) was added to the flask and dissolved in 350 mL of toluene under a nitrogen atmosphere, followed by stirring under reflux for 12 hours. After completion of the reaction by adding 200 ml of water, the mixture was extracted three times with 100 ml of dichloromethane, the extract was dried over excess magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 3: 1 (v: v)] to give the compound Inv 6 (19.9 g, 74% yield) as a white solid.

GC-Mass (Theoretical value: 538.28 g / mol, Measured value: 538 g / mol),

3) Step 3: Synthesis of Intermediate 10

Compound 9 (10g, 18mmol) obtained in <Step 2> and Compound 4 (10g, 19mmol) and Pd (PPh ₃ ) ₄ (0.65 g, 0.57 mmol) obtained in <Preparation Example 1> were placed in a flask, and a nitrogen atmosphere. After dissolving in 80 mL of toluene, 20 mL of an aqueous solution of potassium carbonate (5 g, 36 mmol) was added thereto, followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was extracted three times with 20 ml of dichloromethane, and the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 3: 1 (v: v)] to give compound 10 (6.13 g, yield 65%) as a white solid.

GC-Mass (Theoretical value: 786.22 g / mol, Measured value: 786 g / mol),

4) Step 4: Synthesis of Inv 33

Compound 10 (6 g, 7.6 mmol), diphenylamine (1.5 g, 9.2 mmol) and Pd (Oac) ₂ (0.05 g, 0.22 mmol) obtained in <Step 3>, BINAP (0.273 g, 0.44 mmol) and potassium Carbonate (3.15 g, 22.8 mmol) was added to the flask and dissolved in 50 mL of toluene under a nitrogen atmosphere, followed by stirring under reflux for 12 hours. The reaction was terminated by addition of 30 ml of water, followed by extraction three times with 20 ml of dichloromethane, and the extract was dried over excess magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 3: 1 (v: v)] to give the compound Inv 33 (4.5 g, 75% yield) as a white solid.

GC-Mass (Theoretical value: 805.35 g / mol, Measured value: 805 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 5.62 (m, 1H), 6.04 (s, 2H), 6.46 (m, 12H), 6.98 to 7.08 (m, 19H), 7.32 (s, 1H), 7.82 to 7.88 (m, 2H), 8.04 (m, 1H), 8.12 to 8.18 (m, 2H), 8.68 (m, 1H), 8.93 (m, 1H), 9.15 (s, 1H)

Synthesis Example 6 Preparation of Compound Inv 44

Compound Inv 61 was synthesized through the reaction route of Scheme 10 below.

Scheme 10

1) Step 1: Synthesis of Intermediate 11

Compound 4 (10 g, 19 mmol) obtained in <Preparation Example 1> and 8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5-phenyl-5H- Pyrido [4,3-b] indole (6.3 g, 17.1 mmol) and Pd (PPh ₃ ) ₄ (0.416 g, 0.38 mmol) were placed in a flask and dissolved in 80 mL of toluene under a nitrogen atmosphere, followed by potassium carbonate (4.9 g, 20 mL of an aqueous solution of 38 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours. After the reaction was completed, 30 ml of water was added, followed by extraction three times with 30 ml of dichloromethane. The extract was dried over excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 4: 1 (v: v)] to give compound 11 (5.19 g, yield 70%) as a white solid.

GC-Mass (Theoretical value: 618.12 g / mol, Measured value: 618 g / mol)

2) Step 2: Synthesis of Inv 44

Compound 11 (5 g, 8 mmol), 9H-carbazole (1.6 g, 9.6 mmol) and Pd (Oac) ₂ (0.053 g, 0.24 mmol), BINAP (0.298 g, 0.48 mmol) obtained in <Step 1>above; Potassium carbonate (3.3 g, 24 mmol) was added to the flask and dissolved in 60 mL of toluene under a nitrogen atmosphere, followed by stirring under reflux for 12 hours. The reaction was terminated by addition of 30 ml of water, followed by extraction three times with 30 ml of dichloromethane, and the extract was dried over excess magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 2: 1 (v: v)] to give the compound Inv 44 (3.9 g, 77% yield) as a white solid.

GC-Mass (Theoretical value: 635.24 g / mol, Measured value: 635 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 7.08 to 7.20 (m, 4H), 7.30 to 7.40 (m, 10H), 7.77 to 7.88 (m, 4H), 8.04 to 8.19 (m, 5H ), 8.55 to 8.59 (m, 2H), 8.90 to 8,93 (m, 2H), 9.15 (s, 1H), 9.34 (s, 1H)

Synthesis Example 7 Preparation of Compound Inv 61

Compound Inv 61 was synthesized through the reaction path of Scheme 11 below.

Scheme 11

1) Step 1: Synthesis of Intermediate 12

Compound 4 (10 g, 19 mmol), dibenzofuran-1-boronic acid (3.62 g, 17.1 mmol), and Pd (PPh ₃ ) ₄ (0.416 g, 0.38 mmol) obtained in <Preparation Example 1> were placed in a flask and nitrogen. After dissolving in 80 mL of toluene under an atmosphere, 20 mL of an aqueous solution of Potassium carbonate (4.9 g, 38 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours. After the reaction was completed, 40 ml of water was added and extracted three times with 30 ml of dichloromethane. The extract was dried over excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 2: 1 (v: v)] to give compound 12 (3.25 g, yield 50%) as a white solid.

GC-Mass (Theoretical value: 542.08 g / mol, Measured value: 542 g / mol)

2) Step 2: Synthesis of Inv 61

Compound 12 (3 g, 5.5 mmol), diphenylamine (1.12 g, 6.6 mmol) and Pd (Oac) ₂ (0.037 g, 0.17 mmol) obtained in <Step 1>, BINAP (0.225 g, 0.34 mmol), Potassium carbonate (2.27 g, 16.5 mmol) was added to the flask, dissolved in 50 mL of toluene under nitrogen atmosphere, and stirred under reflux for 12 hours. After the reaction was terminated, the filtered filtrate was concentrated under reduced pressure after the silica gel filter. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 2: 1 (v: v)] to give compound Inv 61 (3.85 g, yield 80%) as a white solid.

GC-Mass (Theoretical value: 561.21 g / mol, Measured value: 561 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 6.46 (m, 4H), 6.98 to 7.08 (m, 7H), 7.19 (m, 1H), 7.31 to 7.39 (m, 3H), 7.54 ( m, 1H), 7.82 to 8.04 (m, 6H), 8.12 to 8.18 (m, 2H), 8.68 (m, 1H), 8.93 (m, 1H), 9.15 (s, 1H)

Synthesis Example 8 Preparation of Compound Inv 63

Compound Inv 63 was synthesized through the reaction path of Scheme 12 below.

[Reaction Scheme 12]

1) Step 1: Synthesis of Intermediate 13

Compound 4 (10 g, 19 mmol), dibenzothiophene-4-boronic acid (3.89 g, 17.1 mmol) and Pd (PPh ₃ ) ₄ (0.416 g, 0.38 mmol) obtained in <Preparation Example 1> were placed in a flask, and nitrogen was added to the flask. After dissolving in 80 mL of toluene under an atmosphere, 20 mL of an aqueous solution of potassium carbonate (4.9 g, 38 mmol) was added thereto, followed by stirring under reflux for 12 hours. After completion of the reaction, 40 ml of water was added, followed by extraction three times with 30 ml of dichloromethane. The extract was dried over excess magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 2: 1 (v: v)] to give compound 13 (5.2 g, yield 78%) as a white solid.

GC-Mass (Theoretical value: 558.06 g / mol, Measured value: 558 g / mol)

2) Step 2: Synthesis of Inv 63

Compound 13 (3.06 g, 5.5 mmol), diphenyl amine (1.12 g, 6.6 mmol) and Pd (Oac) ₂ (0.037 g, 0.17 mmol) obtained in <Step 1>, and BINAP (0.225 g, 0.34 mmol) Potassium carbonate (2.27 g, 16.5 mmol) was added to the flask, dissolved in 50 mL of toluene under nitrogen atmosphere, and stirred under reflux for 12 hours. After the reaction was terminated, the filtered filtrate was concentrated under reduced pressure after the silica gel filter. The crude product was purified by silica gel column chromatography [n-Hexane: Dichloromethane = 2: 1 (v: v)] to give the compound Inv 63 (2.6 g, 85% yield) as a white solid.

GC-Mass (Theoretical value: 577.19 g / mol, Measured value: 577 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz). (Ppm) 6.46 (m, 4H), 6.98-7.08 (m, 7H), 7.32-7.39 (m, 2H), 7.49-7.56 (m, 3H), 7.82 to 7.88 (m, 3H), 8.04 (m, 1H), 8.12 to 8.20 (m, 3H), 8.41 to 8.45 (m, 2H), 8.68 (m, 1H), 8.93 (m, 1H), 9.15 ( s, 1 H)

<Examples 1-14> Fabrication of Organic EL Device

A glass substrate coated with ITO (Indium tin oxide) 1500 thin film was washed by distilled water ultrasonic. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then cleaned the substrate using UV for 5 minutes. The substrate was transferred to a vacuum depositor.

M-MTDATA (60 nm) / each compound synthesized in Synthesis Examples 1-5 (80 nm) / DS-H522 + 5% DS-501 (300 nm) / BCP An organic EL device was manufactured in the order of 10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm). In addition, for the measurement of phosphorescent host performance, each compound synthesized in m-MTDATA (60 nm) / TCTA / Synthesis Examples 6-8 + 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq 3 (30 nm) An organic EL device was manufactured in the order of / LiF (1 nm) / Al (200 nm).

DS-H522 and DS-501 used in device fabrication are manufactured by Doosan Corporation BG, and the structures of m-MTDATA, TCTA, CBP, Ir (ppy) ₃ , and BCP are as follows.

m- MTDATA TCTA

NPB CBP

BCP Ir ( ppy 3

Comparative Example 1 Fabrication of Organic EL Device

An organic EL device was manufactured in the same manner as in Example 1, except that NPB was used as a light emitting host material instead of the compound prepared in Synthesis Example, when forming the hole transport layer.

Comparative Example 2 Fabrication of Organic EL Device

An organic EL device was manufactured in the same manner as in Example 1, except that CBP was used as a light emitting host material, instead of the compound prepared in Synthesis Example, to form an emission layer.

< Experimental Example  1> organic Field  Performance evaluation of light emitting device

For each organic EL device manufactured in Examples 1 to 8 and Comparative Examples 1 and 2, the driving voltage, current efficiency, and luminance at the emission peak were respectively measured, and the results are shown in Table 1 below.

device HTL Voltage (V) Brightness (cd / m ² ) EL peak (nm) Current efficiency (cd / A) Comparative Example 1 NPB 5.2 1816 521 18.1 Example 1 Inv 1 4.7 2363 522 23.6 Example 2 Inv 3 4.9 2273 519 22.7 Example 3 Inv 6 4.8 2205 522 22.1 Example 4 Inv 30 5.1 2120 521 21.2 Example 5 Inv 33 5.2 2015 521 20.2

As can be seen from the results of Table 1, in Examples 1 to 5 in which the triphenylene compound according to the present invention is used as the hole transporting layer of the green organic EL device, a blue organic EL device using a conventional NPB (Comparative Example 1 In comparison,) shows improved performance in terms of efficiency and voltage. In addition, the improvement of the lifetime can be expected through the improvement of the glass transition temperature (T _g ) value.

device HOST Voltage (V) Brightness (cd / m ² ) EL peak (nm) Current efficiency (cd / A) Comparative Example 2 CBP 6.93 445 516 38.2 Example 6 Inv 44 6.12 430 518 39.5 Example 7 Inv 61 6.82 455 520 40.4 Example 8 Inv 63 6.45 479 520 44.6

Similarly, in Examples 6 to 8 in which the compound according to the present invention is used as the light emitting layer of the phosphorescent green organic EL device, in terms of luminous efficiency and driving voltage in comparison with the conventional green organic EL device (Comparative Example 2) using CBP It can be seen that the improved performance is shown in Table 2 (see Table 2).

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, and that various changes and modifications may be made without departing from the scope of the invention. It is natural to belong.

Claims (7)

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

Where
A is a single bond, phenyl, naphthyl, substituted or unsubstituted heteroaryl having 6 to 10 nuclear atoms, wherein the substituent introduced into the hetero aryl is a halogen atom, an alkyl group having 1 to 3 carbon atoms and a 6 to 10 carbon atom. Selected from the group consisting of aryl groups;
B is substituted or unsubstituted aryl between C6 and C10, substituted or unsubstituted heteroaryl having 6 to 10 nuclear atoms, wherein the substituent introduced into the aryl or heteroaryl is a halogen atom, an alkyl group having 1 to 3 carbon atoms And an aryl group having 6 to 10 carbon atoms;
In this case, A and B may be the same as or different from each other independently,
X is one of N, O, S,
l, m are each independently 0 or 1, where X is O or S, then one of l and m is 0,
n is an integer of 1 or 2,
Ar ₁ to Ar ₄ is substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted heteroaryl having 5 to 20 nuclear atoms, wherein the substituents introduced into aryl, heteroaryl are deuterium or halogen atoms, carbon atoms 1 It is selected from the group consisting of an alkyl group of ˜3, an aryl group having 6 to 10 carbon atoms, each may be the same or different independently. The compound of claim 1, wherein the compound represented by Chemical Formula 1 is represented by the following Chemical Formulas 2 to 4.
(2)

(3)

[Chemical Formula 4]

In Chemical Formulas 2 to 4,
A, B, n, Ar ₁ to Ar ₄ are each as defined in claim 1. The compound of claim 1, wherein A or B in Formula 1 is selected from the group of substituents represented by the following Formula 5 when hetero aryl having 6 to 10 nuclear atoms:
[Chemical Formula 5]

A plurality of Z introduced into the substituent group of Chemical Formula 5 may be each independently and may be the same or different from each other even if they are the same. At least one of the plurality of Z is a nitrogen atom, and the rest are carbon atoms. According to claim 1, Ar ₁ and Ar ₂ in Formula 1 may be bonded to each other with A or adjacent substituents to form a condensed ring,
Ar ₃ and Ar ₄ may combine with B or an adjacent substituent to form a condensed ring. anode; cathode; And at least one organic layer interposed between the anode and the cathode, wherein the organic electroluminescent device comprises:
At least one of the said organic layers contains the compound of any one of Claims 1-4, The organic electroluminescent element characterized by the above-mentioned. The organic electroluminescent device according to claim 5, wherein the organic layer is selected from the group consisting of a light emitting layer, an electron transport layer, a hole injection layer, and a hole transport layer. The organic electroluminescent device according to claim 5, wherein the compound is a light emitting layer, an electron transport layer, a hole injection layer, or a hole transport layer material.