KR101674134B1 - triazine derivatives and organic electroluminescent device including the same - Google Patents

triazine derivatives and organic electroluminescent device including the same Download PDF

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KR101674134B1
KR101674134B1 KR1020150058999A KR20150058999A KR101674134B1 KR 101674134 B1 KR101674134 B1 KR 101674134B1 KR 1020150058999 A KR1020150058999 A KR 1020150058999A KR 20150058999 A KR20150058999 A KR 20150058999A KR 101674134 B1 KR101674134 B1 KR 101674134B1
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석문기
김규리
오유진
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(주)더블유에스
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
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    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Abstract

There is provided a triazine derivative represented by the following formula (1).
[Chemical Formula 1]

Figure 112015040859848-pat00027

[Wherein the definition of each substituent in Formula 1 is as defined in the description of the invention]

Description

[0001] The present invention relates to triazine derivatives and organic electroluminescent devices including the same,

TECHNICAL FIELD The present invention relates to a triazine derivative and an organic electroluminescent device including the same. Particularly, a triazine derivative having excellent charge transport properties is very useful as a component of a fluorescent or phosphorescent organic electroluminescent device. Accordingly, the present invention relates to a triazine derivative used for an organic compound layer of an organic electroluminescence device to improve the luminous efficiency by using these.

From the CRT (Cathode Ray Tube), which was the main market of the early display industry, to the LCD (Liquid Crystal Display) which is the most used now, the display industry has developed remarkably over the past few decades.

Nevertheless, the demand for a flat display device having a small space occupancy has been increased due to the recent enlargement of display devices. However, LCD has a disadvantage of requiring a separate light source because its viewing angle is limited and is not a self-luminous type. For this reason, OLEDs (Organic Light Emitting Diodes) have attracted attention as displays using self-emission phenomenon.

In 1963, OLED was first attempted to study the carrier injection type electroluminescence (EL) using a single crystal of anthracene aromatic hydrocarbons by Pope and others. From these studies, it was found that charge injection, recombination, exciton generation, And the basic mechanism of electroluminescence and electroluminescence characteristics.

In addition, after Tang and Van Slyke in 1987 reported the characteristics of high efficiency using a multilayer thin film structure of organic electroluminescent devices [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 913 (1987)], OLEDs have a high potential for use in LCD backlighting and illumination as well as excellent characteristics as a next generation display, and many studies have been conducted under the spotlight [Kido, J., Kimura, M., and Nagai, K., Science 267,1332 (1995)]. Especially, in order to increase the luminous efficiency, various approaches such as structural change and material development have been performed [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

The basic structure of an OLED display generally includes an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer (ETL) ), And a cathode (cathode), and the electron-emitting organic multi-layer film has a sandwich structure formed between both electrodes.

In order for the OLED to emit light properly, electrons in the organic thin film are transported to the light emitting layer with the help of the electron transport layer, and in the anode, holes are transported to the light emitting layer with the help of the hole transport layer, Thereby forming an exciton. The generated excitons drop to a low energy state, and energy is emitted and light of a specific wavelength is generated. At this time, the color of the light changes according to the organic material constituting the light emitting layer, and the organic material of R, G, and B can be used to produce a full color.

Aluminum complexes such as tris (8-hydroxyquinoline) aluminum (III) (Alq 3 ), which has been used since before the multilayer thin film OLEDs announced by Kodak in 1987, Beryllium complexes such as bis (10-hydroxybenzo- [h] quinolinato) beryllium (Bebq 2 ) [T. Sato et al. J. Mater. Chem. 10 (2000) 1151).

Figure 112015040859848-pat00001

In order for OLED to fully exhibit excellent features, it must precede that the material in the device is backed by a stable and efficient material. However, the existing electron transport materials have been limited by the commercialization of OLED, and they are not satisfying the current requirements sufficiently. Therefore, the development of new high performance electron transfer materials is continuously required.

Korean Unexamined Patent Publication No. 2012-0046778 (entitled: Cyclic azine derivatives, a process for their preparation, and an organic electroluminescent device comprising them as constituent elements) Korean Patent Publication No. 2014-0091049 (entitled: Cyclic azine compound having nitrogen-containing cyclic aromatic group, method for producing the same, and organic electroluminescent device comprising the same)

The object of the present invention is to provide a novel triazine derivative having a higher current density and superior durability than a conventional material, and the triazine derivative is contained in an organic film to lower the driving voltage of the device, improve the luminous efficiency, And to provide the extended organic electroluminescent device.

According to one aspect of the present invention, there is provided a triazine derivative represented by the following formula (1).

[Chemical Formula 1]

Figure 112015040859848-pat00002

In Formula 1,

R 1 and R 2 are each independently a substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 5 -C 30 heteroaryl, or a substituted or unsubstituted C 1 -C 30 alkyl to be.

R 3 and R 4 are selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrene, substituted or unsubstituted azaphenanthrene, substituted or unsubstituted azafluorene, Substituted fused azafluorenes, substituted or unsubstituted pyridyls, and substituted or unsubstituted pyrimidinyls.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the triazine derivative.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film includes the triazine derivative .

According to another aspect of the present invention, the triazine derivative is selected from the group consisting of an electron blocking layer, an electron transport layer, an electron injection layer, a functional layer having both an electron transport function and an electron injection function, The organic electroluminescent device is characterized in that it is contained in any one layer.

The triazine derivative according to an embodiment of the present invention may be included in the organic layer of the organic electroluminescent device to lower the driving voltage of the device, improve the luminous efficiency, and prolong the life.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
2 is a graph showing the current density of the organic electroluminescent device manufactured in the comparative test example and the test example.

As used herein, the term "aryl " means a polyunsaturated aromatic hydrocarbon substituent, which may be a single ring or a multiple ring (1 to 3 rings) fused or covalently bonded unless otherwise specified.

The term "heteroaryl" means an aryl group (or a ring) comprising one to four heteroatoms selected from N, O and S (in each case on a separate ring in the case of multiple rings) Optionally oxidized, and the nitrogen atom (s) are quaternized, as the case may be. Heteroaryl groups can be attached to the remainder of the molecule through carbon or heteroatoms.

The aryl includes a single or fused ring system, suitably containing from 4 to 7, preferably 5 or 6, ring atoms in each ring. Also included are structures in which one or more aryls are attached through a chemical bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, But are not limited thereto.

The heteroaryl includes 5- to 6-membered monocyclic heteroaryl and polycyclic heteroaryl fused with one or more benzene rings, and may be partially saturated. Also included are structures in which one or more heteroaryls are attached via a chemical bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt.

Specific examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, Monocyclic heteroaryl such as pyridyl, pyridyl, pyrazinyl, pyridazinyl and the like, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl , Benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, but are not limited thereto. But is not limited thereto.

"Substituted" in the expression " substituted or unsubstituted ", as used herein, means that at least one hydrogen atom in the hydrocarbon is each independently replaced with the same or different substituents. Useful substituents include, but are not limited to:

Such substituents include, but are not limited to, -F; -Cl; -Br; -CN; -NO 2 ; -OH; A C 1 -C 20 alkyl group which is unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO 2 or -OH; A C 1 -C 20 alkoxy group unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO 2 or -OH; C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN , -NO 2, or substituted by -OH or unsubstituted C 6 ~ C 30 aryl group; C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN , -NO 2 or -OH-substituted or unsubstituted C 6 ~ C 30 heteroaryl group, a; C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or unsubstituted C 5 ~ C 20 cycloalkyl group; C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted or unsubstituted by -OH unsubstituted C 5 ~ C 30 heterocycloalkyl group; And a group represented by -N (G 1 ) (G 2 ). Wherein G 1 and G 2 are each independently selected from the group consisting of hydrogen; A C 1 -C 10 alkyl group; Or a C 6 -C 30 aryl group substituted or unsubstituted with a C 1 -C 10 alkyl group.

Hereinafter, the present invention will be described in detail.

The triazine derivative according to one embodiment of the present invention may be represented by the following formula (1).

[Chemical Formula 1]

Figure 112015040859848-pat00003

In Formula 1,

R 1 and R 2 are each independently a substituted or unsubstituted C 6 -C 30 aryl, a substituted or unsubstituted C 5 -C 30 heteroaryl, or a substituted or unsubstituted C 1 -C 30 alkyl to be.

Preferably, R 1 and R 2 in the general formula (1) are each independently phenyl or naphthyl.

Wherein R 3 and R 4 are selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrene, substituted or unsubstituted azaphenanthrene, substituted or unsubstituted azafluorene , Substituted or unsubstituted fused azafluorenes, substituted or unsubstituted pyridyl, and substituted or unsubstituted pyrimidinyl.

Preferably, the substituent in the substituted or unsubstituted pyridyl at R 3 and R 4 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and substituted or unsubstituted quinoline Lt; / RTI >

In R 3 and R 4 , the substituent in the substituted or unsubstituted pyrimidyl may be substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl.

Specific examples of the compound represented by the formula (1) of the present invention include those represented by the following formula (2). However, the compound represented by formula (1) of the present invention is not limited to the compounds of formula (2).

(2)

Figure 112015040859848-pat00004

Figure 112015040859848-pat00005

Figure 112015040859848-pat00006

Figure 112015040859848-pat00007

Figure 112015040859848-pat00008

The triazine derivative represented by the above formula (1) can be synthesized using a known organic synthesis method. The method for synthesizing the triazine derivative can be easily recognized by those skilled in the art with reference to the following production examples.

Also, according to the present invention, there is provided an organic electroluminescent device comprising the triazine derivative represented by the above formula (1).

The triazine derivative of Formula 1 is useful as an electron transport layer material and can be used as a material for various other layers of organic electroluminescent devices.

The organic electroluminescent device according to the present invention includes a first electrode, a second electrode, and at least one organic film disposed between the electrodes. The organic film may be formed by a method in which the pyridyl group represented by Formula 1 is bonded And at least one triazine derivative.

The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one layer selected from the group consisting of functional layers having at the same time.

For example, the triazine derivative may be included in at least one selected from the group consisting of a light emitting layer, an organic layer disposed between the anode and the light emitting layer, and an organic layer disposed between the light emitting layer and the cathode. Preferably, the triazine derivative may be contained in at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, and a functional layer having both a hole injecting function and a hole transporting function. The triazine derivative may be contained in the organic film as a single substance or a combination of different substances. Alternatively, the triazine derivative may be used in combination with a conventionally known compound such as a light emitting layer, a hole transporting layer, and a hole injecting layer.

The organic electroluminescent device according to the present invention can be applied to an organic electroluminescent device including a positive electrode / a light emitting layer / a cathode, a positive electrode / a hole injecting layer / a light emitting layer / a negative electrode, an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / / Light emitting layer / electron transporting layer / electron injecting layer / cathode structure. Alternatively, the organic electroluminescent device may include a functional layer / a light emitting layer / an electron transporting layer / a cathode having both an anode / hole injecting function and a hole transporting function, a functional layer / a light emitting layer / an electron transporting layer / Electron injecting layer / cathode structure, but the present invention is not limited thereto.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

The organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and an organic film including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer is formed thereon And then depositing a material which can be used as a cathode thereon. In addition to such a method, an organic electroluminescent device may be formed by sequentially depositing a cathode material, an organic film, and a cathode material on a substrate.

Meanwhile, the organic layer may be prepared by a wet process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer by using various polymer materials instead of a vapor deposition method.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

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

Example  1: Synthesis of compound (2-1)

The synthesis route of the compound (2-1) is shown below.

Figure 112015040859848-pat00009

Compound (1) 0.5 g (1.07 mmol ), compound (2) 0.36 g (1.62 mmol ), Pd (PPh 3) 4 0.06g (0.05mmol), K 2 CO 3 A mixture of 0.45 g (3.24 mmol) of water, 10 mL of water, 10 mL of toluene (Toluene), and 15 mL of THF was refluxed for 6 hours. After the reaction mixture was cooled to room temperature, the organic layer was separated and concentrated under reduced pressure. The residue was dissolved in 100 mL of dichloromethane, washed with 100 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. Concentrated residue and the compound (3) 0.30 g (0.93 mmol ), Pd (PPh 3) 4 0.03 g (0.03 mmol), 2M K 2 CO 3 A mixture of 1 mL (2.0 mmol), 4 mL water, 10 mL toluene (Toluene), and 4 mL EtOH was refluxed for 12 hours. The reaction mixture was diluted with 50 mL of dichloromethane, washed with 50 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 0.12 g (yield: 29%) of the compound (2-1).

Example  2: Synthesis of compound (2-2)

The synthesis route of the compound (2-2) is shown below.

Figure 112015040859848-pat00010

Compound (4) 5.0 g (9.7 mmol ), compound (5) 1.8 g (10.7 mmol ), Pd (PPh 3) 4 0.34g (0.29 mmol), K 2 CO 3 A mixture of 2.8 g (20.0 mmol) of water, 100 mL of water, 150 mL of toluene (Toluene), and 100 mL of THF was refluxed for 12 hours. This compound in (6) 3.8 g (11.7 mmol ) and 2M K 2 CO 3 10 mL (20.0 mmol) was added thereto, followed by reflux stirring for 12 hours. After the reaction mixture was cooled to room temperature, the organic layer was separated and concentrated under reduced pressure. The residue was dissolved in dichloromethane (200 mL), washed with 200 mL of water, dried over anhydrous magnesium sulfate, filtered, concentrated and purified by column chromatography to give compound (2-2) 2.88 g (Yield: 47%) was obtained.

Example  3: Synthesis of compound (2-3)

The synthesis route of the compound (2-3) is shown below.

Figure 112015040859848-pat00011

Compound (7) 0.44 g (0.85 mmol ), compound (8) 0.30 g (0.93 mmol ), Pd (PPh 3) 4 0.03g (0.03 mmol), 2M K 2 CO 3 A mixture of 1 mL (2.0 mmol), 4 mL water, 10 mL toluene (Toluene), and 4 mL EtOH was refluxed for 12 hours. The reaction mixture was diluted with 50 mL of dichloromethane, washed with 50 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 0.30 g (yield: 56%) of the compound (2-3).

Example  4: Synthesis of compound (2-4)

The synthesis route of the compound (2-4) is shown below.

Figure 112015040859848-pat00012

Compound (7) 0.44 g (0.85 mmol ), compound (3) 0.30 g (0.93 mmol ), Pd (PPh 3) 4 0.03g (0.03 mmol), 2M K 2 CO 3 A mixture of 1 mL (2.0 mmol), 4 mL water, 10 mL toluene (Toluene), and 4 mL EtOH was refluxed for 12 hours. The reaction mixture was diluted with 50 mL of dichloromethane, washed with 50 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 0.35 g of the compound (2-4) (yield: 66%).

Example  5: Synthesis of compound (2-13)

The synthesis route of the compound (2-13) is shown below.

Figure 112015040859848-pat00013

Compound (4) 5.0 g (9.7 mmol ), compound (2) 2.6 g (11.7 mmol ), Pd (PPh 3) 4 0.34g (0.29 mmol), K 2 CO 3 A mixture of 2.8 g (20.0 mmol) of water, 100 mL of water, 150 mL of toluene (Toluene), and 100 mL of THF was refluxed for 20 hours. This compound in (6) 3.1 g (9.7 mmol ) and 2M K 2 CO 3 10 mL (20.0 mmol) was further added and the mixture was refluxed and stirred for 20 hours. After the reaction mixture was cooled to room temperature, the organic layer was separated and concentrated under reduced pressure. The residue was dissolved in dichloromethane (200 mL), washed with 200 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 3.48 g of the compound (2-13) (yield: 53%).

Example  6: Synthesis of compound (2-14)

The synthesis route of the compound (2-14) is shown below.

Figure 112015040859848-pat00014

Compound (7) 0.44 g (0.85 mmol ), compound (9) 0.30 g (0.93 mmol ), Pd (PPh 3) 4 0.03g (0.03 mmol), 2M K 2 CO 3 A mixture of 1 mL (2.0 mmol), 4 mL water, 10 mL toluene (Toluene), and 4 mL EtOH was refluxed for 12 hours. The reaction mixture was diluted with 50 mL of dichloromethane, washed with 50 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 0.30 g (yield: 56%) of the compound (2-14).

Example  7: Synthesis of compound (2-15)

The synthesis route of the compound (2-15) is shown below.

Figure 112015040859848-pat00015

Compound (1) 1.0 g (2.14 mmol ), compound (2) 0.71 g (3.21 mmol ), Pd (PPh 3) 4 0.11g (0.10 mmol), K 2 CO 3 A mixture of 0.89 g (6.42 mmol), 20 mL water, 20 mL toluene (Toluene), and 30 mL THF was refluxed for 6 hours. After the reaction mixture was cooled to room temperature, the organic layer was separated and concentrated under reduced pressure. The residue was dissolved in 100 mL of dichloromethane, washed with 100 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. Concentrated residue and the compound (9) 0.64 g (1.42 mmol ), Pd (PPh 3) 4 0.05g (0.04 mmol), 2M K 2 CO 3 A mixture of 1.3 mL (2.6 mmol), 20 mL water, 20 mL toluene (Toluene), and 30 mL THF was refluxed for 6 hours. The reaction mixture was diluted with 100 mL of dichloromethane, washed with 100 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 0.35 g (yield: 40%) of the compound (2-15).

Example  8: Synthesis of compound (2-16)

The synthesis route of the compound (2-16) is shown below.

Figure 112015040859848-pat00016

Compound (1) 1.0 g (2.14 mmol ), compound (2) 0.71 g (3.21 mmol ), Pd (PPh 3) 4 0.11g (0.10 mmol), K 2 CO 3 0.89g (6.42 mmol), water 20 mL, toluene (Toluene) 20 mL, and then stirred for 6 hours under reflux the mixture of 30 mL THF, compound (8) 0.33 g (1.03 mmol ) and 2M K 2 CO 3 1.1 mL (2.2 mmol) was added and the mixture was refluxed with stirring for 12 hours. The reaction mixture was diluted with 100 mL of dichloromethane, washed with 100 mL of water, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography to obtain 0.37 g (yield: 26%) of the compound (2-16).

Example  9: Synthesis of compound (2-25)

The synthesis route of the compound (2-25) is shown below.

Figure 112015040859848-pat00017

Pd (PPh 3 ) 4 ) was dissolved in 30 mL of toluene, 10 mL of ethanol and 10 mL of water, and 3.00 g (4.91 mmol) of the compound (10) and 1.40 g 283 mg (245 μmol) of potassium tertiary phosphate (K 3 PO 4 ) and 3.12 g (14.7 mmol) of potassium tertiary phosphate were added thereto, followed by stirring at 80 ° C. for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, 80 mL of dichloromethane and 50 mL of water were added to separate the organic layer, and the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography to obtain 2.30 g (yield: 67.9%) of a white solid compound (2-25).

Example  10: Synthesis of compound (2-26)

The synthesis route of the compound (2-26) is shown below.

Figure 112015040859848-pat00018

Pd (PPh 3 ) 4 ) was dissolved in 30 mL of toluene, 10 mL of ethanol and 10 mL of water, and 3.00 g (5.85 mmol) of the compound (12) and 1.51 g 338 mg (293 μmol) of potassium tertiary phosphate (K 3 PO 4 ) and 3.73 g (17.6 mmol) of potassium tertiary phosphate were added thereto, followed by stirring at 80 ° C. for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, 80 mL of dichloromethane and 50 mL of water were added to separate the organic layer, and the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography to obtain 1.17 g (yield: 35.5%) of a white solid compound (2-26).

Example  11: Synthesis of compound (2-27)

The synthesis route of the compound (2-27) is shown below.

Figure 112015040859848-pat00019

To a solution of 2.80 g (4.99 mmol) of the compound (14) and 1.42 g (4.99 mmol) of the compound (15) in 30 mL of toluene, 10 mL of ethanol and 10 mL of water was added tetrakistriphenylphosphine palladium (Pd (PPh 3 ) 4 ) 288 mg (249 μmol) of potassium tertiary phosphate (K 3 PO 4 ) and 3.18 g (15.0 mmol) of potassium tertiary phosphate were added thereto, followed by stirring at 80 ° C. for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, 80 mL of dichloromethane and 50 mL of water were added to separate the organic layer, and the organic layer was washed with water and concentrated under reduced pressure. The resulting reaction mixture was purified by silica gel column chromatography to obtain 1.37 g (yield: 42.9%) of a white solid compound (2-27).

Example  12: Synthesis of compound (2-28)

The synthesis route of the compound (2-28) is shown below.

Figure 112015040859848-pat00020

Compound (10) 3.00 g (4.91 mmol ) and compound (16) 1.27 g (4.91 mmol ) was dissolved in toluene, 30 mL ethanol and 10 mL, water 10 mL tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 283 mg (245 μmol) of potassium tertiary phosphate (K 3 PO 4 ) and 3.12 g (14.7 mmol) of potassium tertiary phosphate were added thereto, followed by stirring at 80 ° C. for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, 80 mL of dichloromethane and 50 mL of water were added to separate the organic layer, and the organic layer was washed with water and concentrated under reduced pressure. The resulting reaction mixture was purified by silica gel column chromatography to obtain 1.72 g (yield: 52.8%) of a white solid compound (2-28).

≪ Test Example 1 >

LC-MS was measured for the compounds of the present invention using a Waters Acquity UPLC H-Class / SQD2 system instrument. The results are shown in Table 1 below.

LC / MS results of the compounds Classification (compound) MS / FAB Calcd. LC-MS / FAB Found Example 1 (Compound 2-1) 678.82 679.58 Example 2 (Compound 2-2) 628.76 629.55 Example 3 (Compound 2-3) 628.76 629.55 Example 4 (Compound 2-4) 628.76 629.62 Example 5 (Compound 2-13) 678.82 679.52 Example 6 (Compound 2-14) 628.76 629.49 Example 7 (Compound 2-15) 678.82 679.58 Example 8 (Compound 2-16) 678.82 679.58 Example 9 (Compound 2-25) 689.80 690.56 Example 10 (Compound 2-26) 563.65 564.49 Example 11 (Compound 2-27) 639.75 640.47 Example 12 (Compound 2-28) 663.77 664.48

≪ Test Example 2 &

The UV / VIS spectra of the compounds of the present invention were measured using a Jasco V-630 instrument and PL (photoluminescence) spectra were measured using a Jasco FP-8500 instrument. The results are shown in Table 2 below.

UV / VIS and PL results of compounds Classification (compound) UV (nm) * 1 PL (nm, room temperature) * 2 Example 1 (Compound 2-1) 259, 270, 317 424 Example 2 (Compound 2-2) 265 411 Example 3 (Compound 2-3) 270 404.5 Example 4 (Compound 2-4) 263, 317 406.5 Example 5 (Compound 2-13) 260, 272 421.5 Example 6 (Compound 2-14) 256 412.5 Example 7 (Compound 2-15) 258 434 Example 8 (Compound 2-16) 255, 273 430.5 Example 9 (Compound 2-25) 255 431.5 Example 10 (Compound 2-26) 269 319 Example 11 (Compound 2-27) 258 409.5 Example 12 (Compound 2-28) 259, 272 430.5 * 1: 1.0 x 10 -5 M in Methylene Chloride
* 2: 5.0 x 10 -6 M in Methylene Chloride

Device fabrication test example

An electron only device (EOD) device was fabricated to confirm the electron mobility for the compounds of the above examples. ITO and Al were used as electrodes in the fabrication of the device. Liq was used to prevent the injection of holes and to inject electrons well, and the compound to be measured was deposited between two Liq.

Comparative Test Example: ITO / Liq / Alq 3  / Liq / Al

The EOD device was deposited by depositing ITO (150 nm) / Liq (2 nm) / Alq 3 (60 nm) / Liq (2 nm) / Al (100 nm) in this order. Organic materials were deposited at a degree of vacuum of 9 × 10 -8 Torr and deposited at a rate of 0.1 Å / sec for Liq, 1 Å / sec for Alq 3 , and 10 Å / sec for Al. The comparative material used in the experiment is Alq 3 . After fabricating the device, it was sealed in a glove box filled with nitrogen gas to prevent air and moisture contact of the device. After the epoxy resin of Nagase Co., Ltd. was dispersed around the ITO substrate, an upper glass plate having a moisture absorbent paper, which was able to remove moisture and the like, was adhered to the ITO substrate and then cured by UV.

Test Example  1: ITO / Liq  / Compound (2-2) / Liq  / Al

In the above comparative test example, a device was fabricated in the same manner as in the above Comparative Test Example, except that the compound (2-2) prepared in Example 2 was used instead of Alq 3 .

Test Example  2: ITO / Liq  / Compound (2-13) / Liq  / Al

In the comparative test example, a device was fabricated in the same manner as in the above comparative test, except that the compound (2-13) prepared in Example 5 was used instead of Alq 3 .

Test Example  3: ITO / Liq  / Compound (2-27) / Liq  / Al

In the comparative test example, a device was fabricated in the same manner as in the above Comparative Test Example except that the compound (2-27) prepared in Example 11 was used instead of Alq 3 .

Test Example  4: ITO / Liq  / Compound (2-28) / Liq  / Al

In the comparative test example, a device was fabricated in the same manner as in the comparative test except that the compound (2-28) prepared in Example 12 was used instead of Alq 3 .

The electrical characteristics of the EOD device manufactured in the comparative test example and the test examples 1 to 4 are shown in Table 3, and the current density according to the voltage for the EOD device manufactured in the comparative test example and the test examples 1 to 4 is shown in FIG. 2 Respectively.

Classification (compound) Current density (mA / cm2) @ 2V Comparative Test Example (Alq 3) 0.02 Test Example 1 (Compound 2-2) 4.39 Test Example 2 (Compound 2-13) 2.18 Test Example 3 (Compound 2-27) 1.75 Test Example 4 (Compound 2-28) 2.36

As can be seen from Table 3 and FIG. 2, when the compounds of the present invention were fabricated using an EOD device, it was confirmed that the devices of Test Examples 1 to 4 had superior current densities to those of the comparative test devices. Such a superior current density increase can lower the driving voltage of the device when fabricating the OLED device, and improve the light emitting efficiency characteristic and the lifetime characteristic.

Claims (10)

A triazine derivative represented by the following formula (1).
[Chemical Formula 1]
Figure 112016099998544-pat00031

[In the above formula (1)
R 1 and R 2 are each independently phenyl or naphthyl,
R < 3 > is naphthyl or phenanthrene,
X 1 to X 4 are each CH or N, and at least one is N.] delete delete delete The method according to claim 1,
Wherein the compound of formula (1) is selected from the group consisting of the following formula (2).
(2)
Figure 112016029878094-pat00022

Figure 112016029878094-pat00023

Figure 112016029878094-pat00024
 An organic electroluminescent device comprising the triazine derivative according to any one of claims 1 to 5. The method according to claim 6,
Wherein the triazine derivative is used as an electron transport layer material. A first electrode, a second electrode, and at least one organic film disposed between the electrodes,
Wherein the organic film comprises the triazine derivative of claim 1 or claim 5. 9. The method of claim 8,
The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one functional layer having at least one functional group at the same time. 9. The method of claim 8,
Wherein the triazine derivative is contained in any one selected from the group consisting of an electron blocking layer, an electron transporting layer, an electron injecting layer, a functional layer having both an electron transporting function and an electron injecting function, and a light emitting layer constituting the organic film The organic electroluminescent device comprising:
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