KR102030388B1 - Asymmetric antracene derivatives having two naphthyl groups and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to an anthracene derivative represented by the following [Formula A] or [Formula B] and an organic light emitting device comprising the same. The substituents X ₁ to X ₇ , Y and Z are the same as defined in the detailed description of the present invention.
[Formula A] [Formula B]

Description

Asymmetric antracene derivatives having two naphthyl groups and organic light-emitting diode including the same}

The present invention relates to an asymmetric anthracene derivative including two naphthyl groups and an organic light emitting device including the same, and more particularly, to an asymmetric anthracene derivative capable of lowering a driving voltage and showing device characteristics with excellent luminous efficiency. It relates to an organic light emitting device comprising.

Recently, as the size of the display device increases, the demand for a flat display device having a small space is increasing. A liquid crystal display, which is a typical flat display device, has a merit of being lighter than a conventional cathode ray tube (CRT). The disadvantage is that the angle is limited and the back light is necessary. In contrast, the organic light emitting diode (OLED), a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. In recent years, application to full-color display or lighting is expected.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.

An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows. Such organic light emitting devices are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

The material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. A host-dopant system can be used as the luminescent material to increase the luminous efficiency through.

The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order for the organic light emitting device to fully exhibit the above-mentioned excellent characteristics, it is supported that a material that forms the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. is supported by a stable and efficient material. It must be preceded.

On the other hand, in the organic light emitting device, charges injected from both electrodes are recombined in the light emitting layer to obtain light emission. However, since the movement speed of the holes is faster than the movement speed of the electrons, a decrease in efficiency due to a part of the holes exiting the light emitting layer is a problem. It becomes Therefore, there is a demand for an electron transport material having a high speed of movement of electrons.

In order to manufacture the organic compound having excellent electron transport ability and hole blocking ability, excellent luminous efficiency and high stability in a thin film state, Korean Patent Publication No. 10-0691543 (2007.03.09) shows four substitution sites of anthracene. An organic compound in which 1 to 2 hetero functional groups are introduced is disclosed. In Korean Patent Application Publication No. 10-2012-0104204 (2012.09.20), an organic compound having a pyridoindole derivative bonded to a substituted anthracene ring structure is described. Japanese Unexamined Patent Publication No. 2010-168363 (2010.08.05) discloses an anthracene derivative having a pyridine naphthyl group having excellent properties of external quantum efficiency and driving voltage.

However, despite efforts to manufacture the electron transporting material for the organic light emitting device as described above, the development of materials for low driving voltage and high light emitting efficiency is not sufficient. The necessity of the development of this excellent material for an electron transport layer for organic light emitting devices is constantly being demanded.

Registered Patent Publication No. 10-0691543 (2007.03.09)

Publication No. 10-2012-0104204 (2012.09.20)

Japanese Laid-Open Patent Publication No. 2010-168363 (2010.08.05)

Therefore, the first technical problem to be achieved by the present invention is to provide an organic compound for an organic light emitting device that can be used for the electron transport layer, and excellent in luminous efficiency having a low voltage driving characteristics.

The second technical problem to be achieved by the present invention is to provide an organic light emitting device including the organic compound.

The present invention provides an anthracene derivative represented by the following [Formula A] or [Formula B] as an organic compound that can be used in the electron transport layer of the organic light emitting device to achieve the first technical problem.

 [Formula A] [Formula B]

In [Formula A] and [Formula B],

Y is the same or different and independently from each other hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero atom having 1 to 50 carbon atoms An aryl group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms;

 Z is the same or different and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted silyl having 1 to 30 carbon atoms Any one selected from the group;

m and m 'are integers from 1 to 8;

When substituents Y and Z are not bonded to carbon of the aromatic ring of the naphthyl group or anthracenyl group, hydrogen is bonded;

X ₁ to X ₇ are the same as or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, substituted or unsubstituted Alkenyl groups having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or Unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 5 to 30 carbon atoms Thioxy group, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted and having hetero atoms as O, N or S A heteroaryl group of a small number of 2 to 50, a cyano group, a nitro group, and any one selected from the group consisting of halogen group, may form a fused ring group of aliphatic, aromatic, aliphatic hetero, or aromatic heterocyclic group which are adjacent to each other;

X ₁ At least one of to X ₇ is a heteroaryl group having 2 to 20 carbon atoms containing a nitrogen atom.

The present invention also includes a first electrode, a second electrode facing the first electrode and an organic layer interposed between the first electrode and the second electrode in order to achieve the second object, the organic layer is Provided is an organic light-emitting device comprising at least one anthracene derivative represented by Formula (A) or (B).

According to the present invention, the anthracene derivative represented by [Formula A] or [Formula B] has a characteristic of low voltage driving and excellent luminous efficiency as compared to the existing material, and can be used for the manufacture of a stable and excellent device. have.

1 is a schematic view of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention provides a compound represented by the following [Formula A] or [Formula B] as an anthracene derivative that can be used in the electron transport layer or the light emitting layer of the organic light emitting device.

[Formula A] [Formula B]

In [Formula A] and [Formula B],

Y is the same or different and independently from each other hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero atom having 1 to 50 carbon atoms An aryl group, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms;

Z is the same or different and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted silyl having 1 to 30 carbon atoms Any one selected from the group;

m and m 'are integers from 1 to 8;

When substituents Y and Z are not bonded to carbon of the aromatic ring of the naphthyl group or anthracenyl group, hydrogen is bonded;

X ₁ to X ₇ are the same as or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, substituted or unsubstituted Alkenyl groups having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or Unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 5 to 30 carbon atoms A thioxy group, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted and having O, N or S as a hetero atom Heteroaryl group, a small number of 2 to 50, cyano, nitro, and any one is selected from a halogen group, may form a fused ring group of aliphatic, aromatic, aliphatic hetero, or aromatic heterocyclic group which are adjacent to each other;

At least one of X ₁ to X ₇ is a heteroaryl group having 2 to 20 carbon atoms including a nitrogen atom;

The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms , Alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms or heteroarylalkyl group having 2 to 24 carbon atoms , Alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, arylsilyl having 1 to 24 carbon atoms It means that the group is substituted with one or more substituents selected from the group consisting of aryloxy group having 1 to 24 carbon atoms.

On the other hand, the aryl group used in the compound of the present invention means an aromatic system consisting of a hydrocarbon containing one or more rings, if there is a substituent may be fused to each other with a neighboring substituent (fused) to further form a ring.

Specific examples of the aryl group may include aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl, and the like, and at least one hydrogen atom of the aryl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, or a silyl group. , Amino group (-NH ₂ , -NH (R), -N (R ') (R''),R' and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, in this case referred to as" alkylamino group " ), Amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group It may be substituted with a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

Heteroaryl group which is a substituent used in the compound of the present invention means a ring aromatic system having 2 to 24 carbon atoms containing 1, 2 or 3 hetero atoms selected from N, O, P or S, and the remaining ring atoms are carbon, The rings may be fused to form a ring. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like. The atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the silyl group which is a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl and methylcyclo Butylsilyl, dimethylfurylsilyl, and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.

More preferably, when at least one of the substituents X ₁ to X ₇ of [Formula A] and [Formula B] is a C2-C20 heteroaryl group containing a nitrogen atom, the heteroaryl group in Formula 1 to Formula 6 It may be any substituent selected.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Structure 5]

 [Structure 6]

Herein, T ₁ to T ₈ in Formulas 1 to 6 are the same or different and independently from each other, C (R ₁₁ ), C (R ₁₁ ) (R ₁₂ ), N, N (R ₁₃ ), O, Any one selected from S; R ₁ to R ₁₃ Are each the same as or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted cyclo group having 3 to 30 carbon atoms An alkyl group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom, wherein each of the structural formulas 1 to In Formula 6, one of R ₁ to R ₁₃ may be a single bond that forms a bond with the naphthyl group in Formulas A and B.

Here, the structural formula 3 may include a compound represented by structural formula 3-1 by a resonance structure according to the movement of electrons.

[Formula 3-1]

Provided that T ₁ to T ₅ and R ₃ and R ₄ are the same as defined above.

Meanwhile, in the present invention, when at least one of X ₁ to X ₇ is a heteroaryl group having 2 to 20 carbon atoms each containing a nitrogen atom, the heteroaryl group may have a plurality of rings. Looking at the case where the heteroaryl group has a plurality of rings, it is divided into a ring of a heteroaryl containing a nitrogen, or a ring of a heteroaryl containing a nitrogen and a ring of an aryl moiety that does not contain a hetero atom. Can lose. In this case, the moiety bonded to the naphthyl groups of Formula A and Formula B may be a ring moiety containing nitrogen or a ring of an aryl moiety containing no nitrogen.

Looking at this through the substituent of the formula 3, in the case of the formula 3 T ₁ to T ₃ is at least one nitrogen atom and T ₄ , T ₅ , R ₃ and R ₄ is an aryl group portion containing no nitrogen The moiety bonded to the naphthyl group of Formula A and Formula B may be any one of T ₁ to T ₃ , or any one selected from T ₄ , T ₅ , R _3, and R ₄ is bonded to the naphthyl group. Can be.

In this case, more preferably, the ring of the aryl group portion not containing nitrogen may be a portion bonded to the naphthyl group in the formula (A) and formula (B).

This may be understood in the same manner as in [Formula 4] to [Formula 6].

In the present invention, Y and Z of the [Formula A] and [Formula B] are the same or different, respectively, independently of each other hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 5 to 20 carbon atoms; M and m 'may be an integer of 1 to 4, respectively.

In this case, only one of the substituents X ₁ to X ₇ of the above [Formula A] and [Formula B] of the present invention may be any one substituent selected from Structural Formulas 1 to 6.

Further, in the present invention, the substituents of Formulas 1 to 6 may each be substituted with 1 to 3 nitrogen atoms in the aromatic carbon site in the substituent to form a heteroaryl group.

When the nitrogen atom is included in the aromatic carbon site, the nitrogen atom may make the aromatic ring system lack electrons, and may serve as an electron transport layer.

More specifically, in the present invention, at least one of the substituents X ₁ to X ₇ of [Formula A] and [Formula B] may be any one of the following substituents 101 to 606.

[Substitution 101] [Substitution 102] [Substitution 103]

[Substitution 104] [Substitution 105] [Substitution 106]

[Substituent 107] [Substituent 108] [Substituent 109]

[Substitution 110] [Substitution 111] [Substitution 112] [Substitution 113]

[Substituent 201] [Substituent 202] [Substituent 203]

[Substituent 204] [Substituent 205] [Substituent 206]

[Substituent 207] [Substituent 208]

[Substituent 301] [Substituent 302] [Substituent 303]

[Substituent 304] [substituent 305] [substituent 306]

[Substituent 307] [Substituent 308]

[Substituent 401] [Substituent 402] [Substituent 403]

[Substituent 404] [Substituent 405] [Substituent 406]

[Substituent 407] [Substituent 408] [Substituent 409]

[Substituent 410] [Substituent 411] [Substituent 412] [Substituent 413]

[Substituent 501] [Substituent 502] [Substituent 503]

[Substituent 601] [Substituent 602] [Substituent 603]

[Substituent 604] [Substituent 605] [Substituent 606]

Wherein R is the same or different and independently from each other, hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, Phosphoric acid or salts thereof, substituted or unsubstituted alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 60 carbon atoms, substituted or unsubstituted carbon atoms 1 Alkoxy group of 60 to 60, substituted or unsubstituted alkylthio group of 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group of 3 to 60 carbon atoms, substituted or unsubstituted aryl group of 6 to 60 carbon atoms, substituted Or unsubstituted aryloxy group having 5 to 60 carbon atoms, substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, substituted or unsubstituted A substituted (alkyl) amino group having 1 to 60 carbon atoms, a di (substituted or unsubstituted alkyl group having 1 to 60 carbon atoms), or a (substituted or unsubstituted aryl having 6 to 60 carbon atoms), di (substituted or unsubstituted groups) Aryl) amino group having 6 to 60 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus and boron, respectively. Substituents of may be fused with groups adjacent to each other to form a ring,

n is an integer from 0 to 9,

When the substituent R is not bonded to the carbon of the aromatic ring in the heteroaryl group of the substituents 101 to 606, hydrogen is bonded.

One of R is a single bond bonded to the naphthyl group of [Formula A] and [Formula B].

In this case, only one of the substituents X ₁ to X ₇ in the [Formula A] and [Formula B] may be any one substituent selected from the substituents 101 to 606 in the present invention.

In addition, the present invention is a first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one of the anthracene derivatives according to the present invention.

In the present invention, "(organic layer) contains at least one organometallic compound" means "(organic layer) one organometallic compound belonging to the scope of the present invention or two different kinds belonging to the category of the organometallic compound. May include the above compounds ".

In this case, the organic layer including the compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a hole injection function and a hole injection function and a functional layer, a light emitting layer, an electron transport layer, and an electron injection layer.

In addition, in the present invention, the organic layer interposed between the first electrode and the second electrode may include an electron transport layer and a light emitting layer, in which case the anthracene derivative of the present invention is included in the electron transport layer, the light emitting layer is a host and a plate It can consist of.

Also, in the present invention, specific examples of the dopant material used in the light emitting layer include pyrene-based compounds, deuterium-substituted pyrene-based compounds, fluorene-based compounds, deuterium-substituted fluorene-based compounds, benzofluorene-based compounds and deuterium-substituted compounds. Benzofluorene compounds, dibenzofluorene compounds, deuterium substituted dibenzofluorene compounds, indenophenanthrene compounds, deuterium substituted indenophenanthrene compounds, arylamines, deuterium substituted arylamines, peryl compounds , Deuterium substituted peryl compound, pyrrole compound, deuterium substituted pyrrole compound, hydrazone compound, deuterium substituted hydrazone compound, carbazole compound, deuterium substituted carbazole compound, stilbene compound, deuterium substituted stilbene type Compounds, starburst compounds, deuterium substituted starburst compounds, oxadiazole compounds, But are coumarin hydrogen substituted oxadiazole-based compound, (coumarine), deuterium-substituted coumarin (coumarine), the present invention is not limited thereby.

Further, as the host used in the light emitting layer, Alq3, CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole)), 9,10-di ( Naphthalen-2-yl) anthracene (ADN), TCTA, TPBI (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (1,3,5-tris (N-phenylbenzimidazole-2- yl) benzene)), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene), E3, DSA (distyrylarylene), dmCBP (see formula below) and the hosts described above Deuterium substituents of the compounds may be used, but is not limited thereto.

PVK ADN

When the light emitting layer includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

On the other hand, when the anthracene derivative is used in the electron transport layer in the present invention, the electron transport layer may be used by mixing other types of electron transport compounds in addition to the anthracene derivative of the present invention.

Here, the compound for an electron transport layer different from the anthracene derivative may have a structure of [Formula A] or [Formula B] as the anthracene derivative, but may be a different compound, or the above [Formula A] or [Formula B] May be an anthracene-based derivative having no structure, and a non-anthracene-based compound not having the structure of [Formula A] or [Formula B] may be used as another kind of compound for an electron transport layer.

As a compound for an electron transporting layer which does not have the structure of [Formula A] or [Formula B], a compound having a structure of PBD, BMD, BND, Liq, Alq ₃ or the following Formula [C] which is an oxadiazole derivative can be used. .

[Formula C]

In [Formula C],

Y is a portion in which any one selected from C, N, O and S is directly bonded to the M to form a single bond, and any one selected from C, N, O and S forms a coordination bond to the M A ligand chelated by the single bond and the coordination bond;

M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination with M,

O is oxygen,

A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group having 2 to 20 carbon atoms Alkynyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, and substituted or unsubstituted hetero having 2 to 50 carbon atoms having O, N or S as a hetero atom. Any one selected from aryl groups,

When M is one metal selected from alkali metals, m = 1, n = 0,

When M is one metal selected from alkaline earth metals, m = 1, n = 1, or m = 2, n = 0,

When M is boron or aluminum, any one of m = 1 to 3, and n is any one of 0-2 to satisfy m + n = 3;

The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, It is meant to be substituted with one or more substituents selected from the group consisting of an aryloxy group, an aryl group, a heteroaryl group, germanium, phosphorus and boron.

In the present invention, Y is the same as or different from each other, and may be any one selected from the following [formula C1] to [formula C39], but is not limited thereto.

[Structure C1] [Structure C2] [Structure C3]

[Structure C4] [Structure C5] [Structure C6]

[Structure C7] [Structure C8] [Structure C9] [Structure C10]

[Formula C11] [Formula C12] [Formula C13]

[Formula C14] [Formula C15] [Formula C16]

[Structure C17] [Structure C18] [Structure C19] [Structure C20]

[Structure C21] [Structure C22] [Structure C23]

[Structure C24] [Structure C25] [Structure C26]

[Structure C27] [Structure C28] [Structure C29] [Structure C30]

[Structure C31] [Structure C32] [Structure C33]

[Structure C34] [Structure C35] [Structure C36]

[Structure C37] [Structure C38] [Structure C39]

In [Formula C1] to [Formula C39],

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl Selected from the group, and may be connected to adjacent substituents with alkylene or alkenylene to form a spirogory or fused ring.

When the anthracene derivative in the present invention is mixed with another kind of electron transport compound and used in the electron transport layer, the mixing ratio thereof is 10:90 to 90:10 as weight percent, preferably 25:75 to 75:25.

Meanwhile, in the present invention, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer is a single molecule deposition method or

The organic light emitting device may be formed by a solution process, and the organic light emitting device may be used in a display device, a display device, or a single color or white lighting device.

Hereinafter, the organic light emitting diode of the present invention will be described with reference to FIG. 1.

1 is a cross-sectional view showing the structure of an organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, if necessary, the hole injection layer 30 and the electron The injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to Figure 1 with respect to the organic light emitting device and a manufacturing method of the present invention. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum thermal deposition or spin coating the hole injection layer material on the anode 20 electrode. Subsequently, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30.

Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level because when the hole is introduced into the cathode through the organic light emitting layer is reduced the lifetime and efficiency of the device. . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a cathode forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

In addition, the light emitting layer may be formed of a host and a dopant.

Moreover, according to the specific example of this invention, it is preferable that the thickness of the said light emitting layer is 50-2,000 GPa.

In this case, the dopant used in the emission layer may be a compound represented by the following [Formula 1] or [Formula 2].

[Formula 1] [Formula 2]

In the above [Formula 1] and [Formula 2],

A is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms , A substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, preferably anthracene, pyrene, phenanthrene, indenophenanthrene, chrysene, naphtha Sen, pisene, triphenylene, perylene, pentacene.

In this case, A may be a compound represented by Formula A1 to Formula A10.

[Formula A1] [Formula A2] [Formula A3] [Formula A4] [Formula A5]

[Formula A6] [Formula A7] [Formula A8] [Formula A9] [Formula A10]

Wherein Z1 to Z2 of the formula [A3] is hydrogen, deuterium atom, substituted or unsubstituted C1-C60 alkyl group, substituted or unsubstituted C2-C60 alkenyl group, substituted or unsubstituted C2-C60 Alkynyl groups, substituted or unsubstituted alkoxy groups having 1 to 60 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 60 carbon atoms, substituted or unsubstituted A substituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms Groups, substituted or unsubstituted (alkyl) amino groups having 1 to 60 carbon atoms, di (substituted or unsubstituted alkyl groups having 1 to 60 carbon atoms), or (substituted or unsubstituted aryl having 6 to 60 carbon atoms), di (Substituted or unsubstituted aryl having 6 to 60 carbon atoms) One or more selected from the group consisting of, each of Z ₁ to Z ₂ are the same as or different from each other, and may form a condensed ring with a group adjacent to each other.

In the above [Formula 1],

X ₁ and X ₂ are each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a single bond, X ₁ and X ₂ may be bonded to each other,

Y ₁ and Y ₂ are each independently substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, substituted Or an unsubstituted heteroalkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 24 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 24 carbon atoms, a cyano group, a halogen group, a substituted or unsubstituted carbon atom From 6 to 24 aryloxy groups, substituted or unsubstituted alkylsilyl groups having 1 to 40 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, germanium, phosphorus, boron, deuterium and hydrogen; more selected species and, Y ₁ to Y ₂ each are the same or different each other, may form a fused ring group of the aliphatic, aromatic, aliphatic hetero, or aromatic heterocyclic group which are adjacent to each other It was.

And l and m are each an integer of 1 to 20, n is an integer of 1 to 4.

In addition, in the above [Formula 2],

C _y is substituted or unsubstituted cycloalkyl having 3 to 8 carbon atoms, b is an integer of 1 to 4, and when b is 2 or more, each cycloalkane may be in fused form, and hydrogen substituted with Each may be substituted with deuterium or alkyl and may be the same or different from each other.

B above Is a single bond or-[C (R ₅ ) (R ₆ )] _p- , wherein p is an integer from 1 to 3, and when p is 2 or more, two or more R ₅ and R ₆ are the same or different from each other;

R ₁ , R ₂ , R _3, R ₅ and R ₆ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or Salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted C1-C60 alkyl groups, substituted or unsubstituted C2-C60 alkenyl groups, substituted or unsubstituted C2-C60 alkynyl groups , Substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted carbon number 6 to 60 aryl groups, substituted or unsubstituted aryloxy groups having 5 to 60 carbon atoms, substituted or unsubstituted arylthio groups having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl groups having 2 to 60 carbon atoms, substituted Or beach An alkyl amino group having 1 to 60 carbon atoms, a di (substituted or unsubstituted alkyl having 1 to 60 carbon atoms), or a (substituted or unsubstituted aryl having 6 to 60 carbon atoms), di (substituted or unsubstituted carbon atoms 6 To aryl) amino group of 60 to 60, substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms,

a is an integer of 1 to 4, when a is 2 or more, two or more R ₃ are the same as or different from each other, and when R ₃ is a plurality, each R ₃ may be in a fused form, and n is 1 to 4 Is an integer.

In addition, the amine group bonded to A in [Formula 1] and [Formula 2] may be represented by any one selected from the group represented by the following [substituent 1] to [substituent 52], but is not limited thereto.

[Substituent 1] [Substituent 2] [Substituent 3] [Substituent 4]

[Substitution 5] [Substitution 6] [Substitution 7] [Substitution 8]

[Substitution 9] [Substitution 10] [Substitution 11] [Substitution 12]

[13 substituent] [14 substituents] [15 substituents] [16 substituents]

[Substitution 17] [Substitution 18] [Substitution 19] [Substitution 20]

[Substitution 21] [Substitution 22] [Substitution 23] [Substitution 24]

[Substitution 25] [Substitution 26]

[Substitution 27] [Substitution 28] [Substitution 29] [Substitution 30]

[Substitution 31] [Substitution 32] [Substitution 33] [Substitution 34]

[Substitution 35] [Substitution 36] [Substitution 37] [Substitution 38]

[Substitution 39] [Substitution 40] [Substitution 41] [Substitution 42]

[Substituent43] [Substituent44] [Substituent45] [Substituent46]

[Substituent 47] [Substituent 48] [Substituent 49] [Substituent 50]

[Substitution 51] [Substitution 52]

R in the substituent is the same or different, and independently from each other, hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or its Salts, phosphoric acid or salts thereof, substituted or unsubstituted alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 60 carbon atoms, substituted or unsubstituted An alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms , Substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, Or an unsubstituted (alkyl) amino group having 1 to 60 carbon atoms, a di (substituted or unsubstituted alkyl group having 1 to 60 carbon atoms), or a (substituted or unsubstituted aryl having 6 to 60 carbon atoms), di (substituted or Unsubstituted aryl) amino group having 6 to 60 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron, , Each of 1 to 12 may be substituted, and each substituent may form a condensed ring with a group adjacent to each other.

In the present invention, the host may be a compound represented by the following Formula 1A to Formula 1D.

[Formula 1A]

In Chemical Formula 1A,

Ar _7, Ar ₈ and Ar ₉ are the same as or different from each other, and each independently, a single bond, a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ Heteroaromatic linking groups;

R ₂₁ to R ₃₀ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or Salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted alkyl groups having 1 to 60 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 60 carbon atoms, substituted or unsubstituted Substituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms A group, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, Substituted or unsubstituted (alkyl) amino group having 1 to 60 carbon atoms, di (substituted or unsubstituted alkyl group having 1 to 60 carbon atoms), or (substituted or unsubstituted aryl having 6 to 60 carbon atoms), di (substituted Or an unsubstituted aryl) amino group having 6 to 60 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus and boron. Each substituent may form a condensed ring with a group adjacent to each other;

E, f and g are the same as or different from each other, and each independently an integer of 0 or 1 to 4;

The two sites marked with * of the anthracene may be identical to or different from each other, and may independently combine with the P or Q structure to constitute an anthracene-based derivative selected from Formulas 1Aa-1 to 1Aa-3.

[Formula 1Aa-1] [Formula 1Aa-2] [Formula 1Aa-3]

Here, the 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, of 1 to 24 carbon atoms Alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group, or C2-C24 hetero Arylalkyl group, alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroarylaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, and 1 to 24 carbon atoms It means substituted with one or more substituents selected from the group consisting of an arylsilyl group, an aryloxy group having 1 to 24 carbon atoms.

[Formula 1B]

In Chemical Formula 1B,

Ar ₁₇ to Ar ₂₀ may be the same as or different from each other, and each independently the same substituent as defined in Ar ₇ to Ar ₈ in Formula 1A, and R ₆₀ to R ₆₃ may be defined in R ₂₁ to R ₃₀ of Formula 1A. And the same substituent as described above.

The w and ww are the same or different from each other, the x and xx are the same or different from each other, the w + ww and x + xx values are the same or different from each other and are each independently an integer of 0 to 3. In addition, y and yy are the same as or different from each other, z and zz are the same as or different from each other, and y + yy to z + zz are 2 or less, and are integers of 0 to 2, respectively.

[Formula 1C]

In Chemical Formula 1C,

Ar ₂₁ to Ar ₂₄ may be the same as or different from each other, and each independently the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₄ to R ₆₇ may be selected from R ₂₁ to R ₃₀ of Formula 1A. It consists of the same substituent as defined.

In addition, ee to hh are the same as or different from each other and each independently an integer of 1 to 4, and ii to ll are the same or different from each other and each independently an integer of 0 to 4.

[Formula 1D]

In Chemical Formula 1D,

Ar ₂₅ to Ar ₂₇ are the same as or different from each other, and each independently include the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₈ to R ₇₃ are the same as or different from each other, and each independently It consists of the same substituent as defined in R <_21> -R <_30> of 1A, and each substituent may form a saturated or unsaturated cyclic structure with adjacent ones. In addition, the mm to ss are the same as or different from each other and are each independently an integer of 0 to 4.

More specifically, the host may be represented by any one selected from the group represented by [Compound 1] to [Compound 56], but is not limited thereto.

[Compound 1] [Compound 2] [Compound 3] [Compound 4]

[Compound 5] [Compound 6] [Compound 7] [Compound 8]

[Compound 9] [Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15] [Compound 16]

[Compound 17] [Compound 18] [Compound 19] [Compound 20]

[Compound 21] [Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27] [Compound 28]

[화합물29] [화합물30] [화합물31] [화합물32]

[Compound 29] [Compound 30] [Compound 31] [Compound 32]

[Compound 33] [Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39] [Compound 40]

[Compound 41] [Compound 42] [Compound 43] [Compound 44]

[Compound 45] [Compound 46] [Compound 47] [Compound 48]

[Compound 49] [Compound 50] [Compound 51] [Compound 52]

[Compound 53] [Compound 54] [Compound 55] [Compound 56]

In addition to the dopant and the host, the emission layer may further include various hosts and various dopant materials.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited thereby.

<Example>

Synthesis Example 1. Synthesis of [Compound 1]

Synthesis Example 1-1) Synthesis of (10- (naphthalen-1-yl) anthracene-9-yl) boronic acid

Synthesis Example 1-1-a) Synthesis of 9- (naphthalen-1-yl) anthracene

In a round bottom flask, 27.2 g (158 mmol) of 1-naphthalene boronic acid, 34 g (132 mmol) of 9-bromoanthracene, 36.6 g (264 mmol) of potassium carbonate, 3 g (2 mmol) of Pd (PPh ₃ ) ₄ , 70 ml of water, 180 ml of toluene and 180 ml of tetrahydrofuran were added and refluxed.

After the completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, and 27.2 g (yield 81%) of 9- (naphthalen-1-yl) anthracene was obtained by column chromatography.

Synthesis Example 1-1-b) Synthesis of 9-bromo-10- (naphthalen-1-yl) anthracene

27.2 g (0.108 mol) of 9- (naphthalen-1-yl) anthracene prepared in Synthesis Example 1-1-a) and 250 ml of dichloromethane were added to a round bottom flask to dissolve the crystals at room temperature, and then cooled to 0 ° C. Then, 17.2 g of bromine (0.107 mol) was diluted in 50 ml of dichloromethane and reacted slowly. After completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, crystals were precipitated with methanol and recrystallized to give 26 g of yellow 9-bromo-10- (naphthalen-1-yl) anthracene crystal (76% yield). )

Synthesis Example 1-1-c) Synthesis of (10-naphthalen-1-yl) anthracene-9-yl) boronic acid

In a round bottom flask, 9-bromo-10- (naphthalen-1-yl) anthracene (26 g, 68 mmol) prepared in Synthesis Example 1-1-b was dissolved in 210 mL of THF. N-butyllithium (51 mL) was slowly added while cooling to -78 ° C. After the addition, the mixture was stirred at −78 ° C. for about 1 hour, and trimethyl borate (33.1 g, 95 mmol) was added thereto. After stirring at −78 ° C. for 1 hour, the mixture was stirred at room temperature for about 2 hours, and 2N hydrochloric acid solution was added to adjust acidity. Crystals were extracted with hexane, followed by extraction with EA, and solvents were removed to obtain 18 g (yield 76.2%) of (10-naphthalen-1-yl) anthracene-9-yl) boronic acid.

Synthesis Example 1-2) Synthesis of 8-iodonaphthalen-2-yl trifluoromethanesulfonate

Synthesis Example 1-2-a) Synthesis of 8-iodo-2-naphthol

Scheme 1-2-a)

In a round bottom flask, 100 g (628 mmol) of 8-amino-2-naphthol is dissolved in 300 mL of acetic acid, cooled to 0 ° C., and 200 mL of sulfuric acid is slowly added dropwise. After completion of the dropwise addition, 52 g (754 mmol) of sodium nitrite was added dropwise to water, stirred for 1 hour at the same temperature, and then heated to room temperature. Then, 3 g of ice and urea were added thereto, and cooled to 0 ° C. do. After the addition was completed, the mixture was stirred at room temperature, treated with sodium thiosulfate, extracted, concentrated, and separated by column to obtain 8-iodo-2-naphthol. (105 g, 61.9% yield)

Synthesis Example 1-2-b) Synthesis of 8-iodonaphthalen-2-yl trifluoromethanesulfonate

Scheme 1-2-b)

19.6 g (73 mmol) of 8-iodo-2-naphthol obtained in Synthesis Example 1-2-a) was added to a round bottom flask, and dissolved with dichloromethane. Then, 7 mL (87 mmol) of pyridine was added and cooled to 0 ° C. .

Anhydrous 14.7 mL (87 mmol) of trifluoromethanesulphonic was slowly added dropwise, and when completed, the mixture was warmed to room temperature and stirred sufficiently. (22 g, yield 75.3%)

Synthesis Example 1-3 Synthesis of 8- (10- (naphthalen-1-yl) anthracene-9-yl) naphthalen-2-yl trifluoromethane sulfonate

Scheme 1-3)

In a round bottom flask, 22 g (55 mmol) of 8-iodonaphthalen-2-yl trifluoromethanesulfonate prepared in Synthesis Example 1-2), (10- ( Naphthalen-1-yl) anthracene-9-yl) boronic acid 21.9 g (60 mmol) tetrakis (triphenylphosphine) palladium (0) 1.27 g, (1 mmol) potassium carbonate 15.2 g (109 mmol) tetrahydrofuran Add 110 mL of toluene, 110 mL of toluene, and 44 mL of water to reflux. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with ethyl acetate / water, the organic layer was concentrated and column separated to obtain a product. (24 g, 80% yield)

Synthesis Example 1-4) Synthesis of [Compound 1]

5.2 g (9 mmol) of 8- (10- (naphthalen-1-yl) anthracene-9-yl) naphthalen-2-yl trifluoromethanesulfonate prepared in Synthesis Example 1-3) in a round bottom flask, (1H-1,2,4-triazol-1-yl) boronic acid 1 g (9 mmol), tetrakis (triphenylphosphine) palladium (0) 0.4 g, potassium carbonate 3.3 g, ethanol 25 mL, toluene Add 25 mL of water and 10 mL of reflux. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with ethyl acetate / water, the organic layer was concentrated and separated by column to synthesize [Compound 1]. (2.7 g, yield 60%)

MS (MALDI-TOF): m / z 498 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

119.6,122.4,125.4,125.6,126.3,127.2,128.3,128.4,129,130.9,131.6,131.8,133.1,134.2,143.3,153.6 [36C]

Synthesis Example 2. Synthesis of [Compound 2]

Using the same method as in Synthesis Example 1, except that 6-quinoxaline boronic acid was used instead of (1H-1,2,4-triazol-1-yl) boronic acid used in Synthesis Example 1-4) [ Compound 2] was synthesized. (3.5 g, yield 50%)

MS (MALDI-TOF): m / z 575 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

119.6,125.1,125.3,125.4,125.6,126.3,127.1,127.2,127.9,128.3,128.8,129,130.9,131.8,133.1,133.6,134.1,134.2,138.1,140.8,141.1,142.7,144.8 [43C]

Synthesis Example 3. Synthesis of [Compound 3]

5-amino-2-naphthol was used instead of 8-amino-2-naphthol used in Synthesis Example 1-2-a, and (1H-1,2,4-triazole used in Synthesis Example 1-4). [Compound 3] was synthesized in the same manner as in Synthesis Example 1, except that 2-pyrimidinylboronic acid was used instead of -1-yl) boronic acid. (2.7 g, 47% yield)

MS (MALDI-TOF): m / z 509 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

117.7,119.6,124.7,125.4,125.6,126.3,127.2,128.3,129,130.9,131.8,132.8,133.1,133.9,134.2,134.7,137.7,156.1,164.2 [38C]

Synthesis Example 4. Synthesis of [Compound 4]

The same method as in Synthesis Example 1-1) was used except that (6-methylnaphthalen-1-yl) boronic acid was used instead of 1-naphthalene boronic acid used in Synthesis Example 1-1-a). [Compound 4] was synthesized by the same method except that 8-quinolinyl boronic acid was used instead of (1H-1,2,4-triazol-1-yl) boronic acid used in Example 1-4) It was. (3.2 g, yield 43%)

MS (MALDI-TOF): m / z 572 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

21.5,118.5,119.6,121.5,125.1,125.2,125.4,125.6,126.2,126.6,127.2,127.5,127.6,127.8,128.1,129,130.2,130.9,131.1,131.2,131.3,131.8,132,132.8,133.1,134.1,134.7, 136.4,138.1,139.6,146.5,149.9 [44C]

Synthesis Example 5. Synthesis of [Compound 5]

Synthesis Example 5-1) Synthesis of 5- (10- (naphthalen-1-yl) anthracene-9-yl) naphthalen-1-yl trifluoromethane sulfonate

The same method as in Synthesis Example 1-2) and Synthesis Example 1-3) was performed except that 5-amino-1-naphthol was used instead of 8-amino-2-naphthol used in Synthesis Example 1-2-a). To obtain the product. (7.5 g, 70% yield)

Synthesis Example 5-2) Synthesis of 2-methyl-2H-1,2,3-benzotriazole-5-boronic acid

Scheme 5-2)

In a round bottom flask 5-bromo-2-methyl-2H-1,2,3-benzotriazole (8.5 g, 40 mmol) was dissolved in 650 mL of THF. N-BuLi (30 mL) was added slowly while cooling to -78 ° C. After the addition, the mixture was stirred at −78 ° C. for about 1 hour, and trimethyl borate (5.9 g, 56 mmol) was added thereto. After stirring at −78 ° C. for 1 hour, the mixture was stirred at room temperature for about 2 hours, and 2 N HCl was added to adjust acidity. After extraction with EA, the solvent was removed, and crystals were obtained with hexane to obtain a product. (5.5 g, yield 78%)

Synthesis Example 5-3) Synthesis of [Compound 5]

Scheme 5-3)

5.2 g (9 mmol) of 5- (10- (naphthalen-1-yl) anthracene-9-yl) naphthalen-1-yl trifluoromethanesulfonate prepared in Synthesis Example 5-1) in a round bottom flask; 2-methyl-2H-1,2,3-benzotriazole-5-boronic acid 1.6 g (9 mmol) prepared in Synthesis Example 5-2), tetrakis (triphenylphosphine) palladium (0) 0.4 g, potassium carbonate 3.3 g, ethanol 25 mL, toluene 25 mL, water 10 mL was added to reflux. When the reaction was completed, the reaction solution was cooled to room temperature, extracted with ethyl acetate / water, the organic layer was concentrated and separated by column to synthesize [Compound 5]. (2.5 g, yield 68%)

MS (MALDI-TOF): m / z 562 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

43.9,119.6,125.1,125.4,125.6,126.3,127.2,127.4,127.9,128.3,129,130,130.1,130.9,131.8,131.9,133.1,134.2,135.4, 136.5,136.7,144.3,145.5 [41C]

Synthesis Example 6. Synthesis of [Compound 6]

Synthesis Example 6-1. Synthesis of 2,6-dialkyl substituted 10- (naphthalen-1-yl) anthracene-9-yl boronic acid

Synthesis Example 6-1-a) Synthesis of 2,6-dialkyl Substituted Anthracene Derivatives

2-methyl-2-hexanol (35 g, 300 mmol) and anthracene (18.4 g, 100 mmol) were added to 50 mL trifluoroacetic acid and refluxed under nitrogen for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with dichloromethane. The resulting solid is filtered while concentrating the organic layer under reduced pressure, and then separated by column chromatography. Recrystallization with methanol gave the product. (6 g, yield 16%) was obtained.

Synthesis Example 6-1-b) Synthesis of 2,6-dialkyl Substituted 9,10-Dibromoanthracene

2,6-dialkyl substituted anthracene (6 g, 16 mmol) synthesized in Synthesis Example 6-1-a was added to 100 mL dichloroethane and bromine (2.1 mL, 40 mmol) while stirring at room temperature for 4 hours. Was added drop wise. It was poured into water and sodium sulfate was added to consume residual bromine. Then it was extracted with dichloromethane and the organic layer was dried over magnesium sulfate. The resulting material was passed through an alumina column using dichloromethane eluent, then evaporated, and methanol was added to precipitate a pale yellow solid, yielding about 7.2 g of product.

Synthesis Example 6-1-c) Synthesis of 2,6-dialkyl substituted 9-bromo-10- (naphthalen-1-yl) anthracene

In a round bottom flask, 7.2 g (13 mmol) of 2,6-dialkyl substituted 9,10-dibromoanthracene prepared in Synthesis Example 6-1-b), 2.4 g (13 mmol) of 1-naphthalene boronic acid, 3.7 g (27 mmol) of potassium carbonate, 0.3 g (3 mmol) of Pd (PPh ₃ ) ₄ , 15 ml of water, 40 ml of toluene and 40 ml of tetrahydrofuran were added and refluxed.

After the completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, and recrystallized with toluene hexane to obtain a product (5.4 g, yield 70%).

Synthesis Example 6-1-d) Synthesis of 2,6-dialkyl substituted 10- (naphthalen-1-yl) anthracene-9-yl boronic acid

2,6-dialkyl substituted 9-bro, prepared in Synthesis Example 6-1-c) instead of 9-bromo-10- (naphthalen-1-yl) anthracene used in Synthesis Example 1-1-c Boronic acid (7.5 g, yield 78%) was synthesized using the same method except that mother-10- (naphthalen-1-yl) anthracene was used.

Synthesis Example 6-2) Synthesis of 4-iodonaphthalen-1-yl trifluoromethanesulfonate

The product (20 g, yield 76%) was obtained using the same method except that 4-amino-1-naphthol was used instead of 8-amino-2-naphthol used in Synthesis Example 1-2).

Synthesis Example 6-3) 4- (2,6-bis (2-methylhexane-2-yl) -10- (naphthalen-1-yl) anthracene-9-yl) naphthalen-1-yl trifluoromethanesulfo Synthesis of Nate

4-Iodonaphthalen-1-yl trifluoromethanesulfo prepared in Synthesis Example 6-2) instead of 8-iodonaphthalen-2-yl trifluoromethane sulfonate used in Synthesis Example 1-3) 2,6-dialkyl substituted 10- (naphthalen-1-yl) prepared in Synthesis Example 6-1 above using nate and replacing (10- (naphthalen-1-yl) anthracene-9-yl) boronic acid A product (16 g, yield 75%) was obtained using the same method except that anthracene-9-yl boronic acid was used.

Synthesis Example 6-4) Synthesis of [Compound 6]

4- (2,6) prepared in Synthesis Example 6-3 instead of 8- (10-phenylanthracene-9-yl) naphthalen-2-yl trifluoromethanesulfonate used in Synthesis Example 1-4) -Bis (2-methylhexane-2-yl) -10- (naphthalen-1-yl) anthracene-9-yl) naphthalen-1-yl trifluoromethane sulfonate, and (1H-1,2, 2.0 g (yield 45%) of [Compound 6] was obtained using the same method except that (1,10-phenanthroline-5-yl) boronic acid was used instead of 4-triazol-1-yl) boronic acid. Synthesized.

MS (MALDI-TOF): m / z 838 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

14.1,23.3,26.4,29.1,38,44.4,119.6,120.1,121.5,122.3,123.5,124.7,125.4,126.3,127.2,128.3,128.4,129.6,130.3,130.7,131,131.6,131.8,131.9,132.9,133.1, 133.9,134.2,135.7,136.4,137,147.3,149.9,154.6 [62C]

Synthesis Example 7. Synthesis of [Compound 7]

Synthesis Example 7-1) Synthesis of 2,3-dibromonaphthalen-1-amine

Scheme 7-1

125 g (873 mmol) of 1-aminonaphthalene and 445 mL of acetic acid were added to a round bottom flask, and the temperature of the reactor was cooled to 0 ° C. The bromine is diluted in 890 mL of acetic acid and added dropwise to the reactor and when complete, the temperature is raised to 60 ° C. and stirred for 1 hour. At the end of the reaction, the temperature of the reactor is lowered to room temperature and the resulting salt is filtered off. The filtered salt is added to an aqueous sodium hydroxide solution and stirred. The resulting solid is filtered and column separated. (145 g, 55%)

Synthesis Example 7-2) Synthesis of 5-bromonaphtho [1,2-d] [1,2,3] oxadiazole

Scheme 7-2)

60 g (200 mmol) of 2,3-dibromonaphthalene-1-amine prepared in Synthesis Example 7-1) and 900 mL of acetic acid were added to a round bottom flask, and cooled to 0 ° C., 150 mL of propionic acid was added thereto. Add and stir. Then, add 16 g of sodium nitrite, stir for 30 minutes, and pour the reaction solution into ice water. The resulting solid is filtered, further water is added to the filtrate, stirred and filtered. (24 g, 46%)

Synthesis Example 7-3) Synthesis of 4-bromo-2-naphthol

Scheme 7-3)

Into a round-bottom flask, 24 g (95 mmol) of 5-bromonaphtho [1,2-d] [1,2,3] oxadiazole prepared in Synthesis Example 7-2) under nitrogen stream was added and 500 mL of ethanol Dissolve in. 1.16 g of sodium borohydride are placed in a reactor and stirred for 12 hours. An aqueous hydrochloric acid solution containing 28 mL of hydrochloric acid was added dropwise to the reactor and stirred for 1 hour. At the end of the reaction, neutralize by adding 10% aqueous sodium hydroxide solution. After neutralization is completed, the mixture is extracted with dichloromethane and water, and the organic layer is concentrated. The column is purified and recrystallized. (17 g, 78%)

Synthesis Example 7-4) Synthesis of 4-bromonaphthalen-2-yl trifluoromethanesulfonate

Scheme 7-4

14.5 g (65 mmol) of 4-bromo-2-naphthol synthesized in Synthesis Example 7-3) was added to a round bottom flask, and dissolved with dichloromethane. Then, pyridine 5.7 g (72 mmol) was added thereto and cooled to 0 ° C. . 15.8 g (85 mmol) of trifluoromethanesulphonic anhydride is slowly added dropwise, and when complete, the mixture is warmed to room temperature and stirred sufficiently. After confirmation by TLC, 2 M hydrochloric acid is added, stirred, extracted, concentrated, and separated by column. (20 g, 86.7%)

Synthesis Example 7-5) Synthesis of 5-bromo-1,2-diphenyl-1H-benzimidazole

4-methylbenzenesulfonic acid (3.1 g, 16 mmol) with N ¹ -benzyl-4-bromobenzene-1,2-diamine (45 g, 160 mmol), 500 mL of dichloromethane and 30 mL of trimethylorthobenzoate It is added to the mixed solution and reacted for about 40 hours at room temperature under nitrogen. After the reaction was completed, the organic layer was concentrated under reduced pressure, washed with 40% methanol / water and sodium hydrogencarbonate / water, and dried to obtain a product. (22.3 g, yield 40%)

Synthesis Example 7-6) Synthesis of (1,2-diphenyl-1H-benzo [d] imidazol-5-yl) boronic acid

5-Bromo-1,2-diphenyl-1H prepared in Synthesis Example 7-5 instead of 9-bromo-10- (naphthalen-1-yl) anthracene used in Synthesis Example 1-1-c) The product was obtained using the same method except that benzimidazole was used (7 g, 35% yield).

Synthesis Example 7-7) Synthesis of 5- (4-bromonaphthalen-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole

4 prepared in Synthesis Example 7-4 instead of 8- (10- (naphthalen-1-yl) anthracene-9-yl) naphthalen-2-yl trifluoromethanesulfonate used in Synthesis Example 1-4) (1, prepared in Synthesis Example 7-6) using bromonaphthalen-2-yl trifluoromethanesulfonate and instead of (1H-1,2,4-triazol-1-yl) boronic acid The product was obtained using the same method except that 2-diphenyl-1H-benzo [d] imidazol-5-yl) boronic acid was used. (7 g, yield 70%)

Synthesis Example 7-8) Synthesis of [Compound 7]

5- (4-bromonaphthalen-2-yl) -1 prepared in Synthesis Example 7-7 instead of 8-iodonaphthalen-2-yl trifluoromethane sulfonate used in Synthesis Example 1-3) [Compound 7] was synthesized in the same manner except for using, 2-diphenyl-1H-benzo [d] imidazole. (3.4 g, yield 48%)

MS (MALDI-TOF): m / z 699 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

114.6,115.7,119.6,122.1,122.9,125.4,125.6,126.3,127.2,127.5,128.2,128.3,129,129.2,129.6,130.9,131,131.1,131.8,132,133.1,134,134.2,134.6,134.7,134.9,137,137.2,138.2,139.4, 143.2,149.4 [53C]

Synthesis Example 8. Synthesis of [Compound 8]

Synthesis Example 8-1) Synthesis of 1,8-di (1,3,4-oxadiazol-2-yl) naphthalene

Scheme 8-1)

1,8-dibromonaphthalene is used instead of 9-bromoanthracene used in Synthesis Example 1-1-a), and (1,3,4-oxadiazol-2-yl) boron instead of phenylboronic acid The product was obtained using the same method except that acid was used (26 g, 71% yield).

Synthesis Example 8-2) Synthesis of 2,2 '-(4-bromonaphthalene-1,8-diyl) bis (1,3,4-oxadiazole)

Scheme 8-2)

In a round bottom flask, 29 g (103 mmol) of 1,8-di (1,3,4-oxadiazol-2-yl) naphthalene prepared in Synthesis Example 8-1) was dissolved in 0.3 L of dichloromethane and 0 Stir at ° C. 18.2 g (114 mmol) of bromine are added dropwise in 0.1 L of dichloromethane. After stirring for about 3 hours at room temperature, the reaction was terminated by adding an aqueous sodium hydrogen carbonate solution, and then the aqueous layer was removed. The organic layers were collected, concentrated, and crystallized with methanol. (25 g, yield 75%)

Synthesis Example 8-3) Synthesis of [Compound 8]

2,2 '-(4-bromonaphthalene-1, prepared in Synthesis Example 8-2) instead of 8-iodonaphthalen-2-yl trifluoromethane sulfonate used in Synthesis Example 1-3) [Compound 8] was synthesized in the same manner except that 8-diyl) bis (1,3,4-oxadiazole) was used. (3.2 g, yield 42%)

MS (MALDI-TOF): m / z 567 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

119.6,122.8,124.7,125.2,125.4,125.6,126.3,127.2,128.3,129,129.2,129.6,129.7,130.9,131.8,133.1,134.2,134.9,136,153.3,164.5 [38C]

Synthesis Example 9. Synthesis of [Compound 9]

Synthesis Example 9-1) Synthesis of 7-chloro-2-phenyl-1-naphthol

Scheme 9-1)

15.3 g (125 mmol) phenyl boronic acid, 34.0 g (132 mmol) 2-bromo-7-chloro-1-naphthol, 36.6 g (264 mmol) potassium carbonate, Pd (PPh ₃ ) ₄ 3 g (2 mmol), 70 ml of water, 180 ml of toluene and 180 ml of tetrahydrofuran were added and refluxed.

After the completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, and 26 g of a product (yield 77%) was obtained by column chromatography.

Synthesis Example 9-2 Synthesis of 2-phenyl-7- (4-pyridinyl) -1-naphthol

Scheme 9-2)

In a round bottom flask, 15.1 g (122 mmol) of 4-pyridinyl boronic acid, 26.0 g (102 mmol) of 7-chloro-2-phenyl-1-naphthol prepared in Synthesis Example 9-1) and 28.3 g of potassium carbonate ( 204 mmol), 2.3 g (1.55 mmol) of Pd (PPh ₃ ) ₄ , 54 ml of water, 140 ml of toluene and 140 ml of tetrahydrofuran were added and refluxed.

After the completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, and 21.7 g of a product (yield 72%) was obtained using column chromatography.

Synthesis Example 9-3) Synthesis of 2-phenyl-7- (4-pyridinyl) naphthalen-1-yl trifluoromethanesulfonate

Scheme 9-3)

Using 2-phenyl-7- (4-pyridinyl) -1-naphthol prepared in Synthesis Example 9-2 instead of 8-iodo-2-naphthol used in Synthesis Example 1-2-b) The product was obtained using the same method except for (21.3 g, yield 68%).

Synthesis Example 9-4) Synthesis of [Compound 9]

2-phenyl-7- (4-pyridinyl) naphthalene- prepared in Synthesis Example 9-3) instead of 8-iodonaphthalen-2-yl trifluoromethane sulfonate used in Synthesis Example 1-3) [Compound 9] was synthesized using the same method except that 1-yl trifluoromethanesulfonate was used (4 g, 55% yield).

MS (MALDI-TOF): m / z 584 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

119.6,120.6,124.6,125.4,125.6,126.1,126.3,127.2,127.6,127.7,127.9,128.3,128.8,129,129.2,129.6,130.9,131.8,133.1,133.6,134.1,134.2,135.6,136.9,137.6,142,147.2, 149.7 [45C]

Synthesis Example 10 Synthesis of [Compound 10]

Synthesis Example 10-1) Synthesis of (10- (naphthalen-2-yl) anthracene-9-yl) boronic acid

Synthesis Example 10-1-a) Synthesis of 9- (naphthalen-2-yl) anthracene

To a round bottom flask was added 2-naphthalene boronic acid 19.4 g (158 mmol), 9- bromo-anthracene 34 g (132 mmol), potassium carbonate 36.6 g (264 mmol), Pd (PPh 3) 4 3 g (2 mmol), 70 ml of water, 180 ml of toluene and 180 ml of tetrahydrofuran were added and refluxed.

After completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, and 32.9 g (yield 80%) of 9- (naphthalen-2-yl) anthracene was obtained using column chromatography.

Synthesis Example 10-1-b) Synthesis of 9-bromo-10- (naphthalen-2-yl) anthracene

32.9 g (0.108 mol) of 9- (naphthalen-2-yl) anthracene prepared in Synthesis Example 10-1-a) and 550 ml of dichloromethane were added to a round bottom flask to dissolve the crystals at room temperature, and then cooled to 0 ° C. After that, 20.2 g (0.126 mol) of bromine was diluted in 100 ml of dichloromethane and reacted slowly. After completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, crystals were precipitated with methanol and recrystallized to give 30.6 g of yellow 9-bromo-10- (naphthalen-2-yl) anthracene crystal (yield 75%). Got

Synthesis Example 10-1-c) Synthesis of (10- (naphthalen-2-yl) anthracene-9-yl) boronic acid

In a round bottom flask, 9-bromo-10- (naphthalen-2-yl) anthracene (30.6 g, 80 mmol) prepared in Synthesis Example 10-1-b) was dissolved in 220 mL of THF. N-butyllithium (60 mL) was slowly added while cooling to -78 ° C. After the addition, the mixture was stirred at −78 ° C. for about 1 hour, and trimethyl borate (11.8 g, 112 mmol) was added thereto. After stirring at −78 ° C. for 1 hour, the mixture was stirred at room temperature for about 2 hours, and 2N hydrochloric acid solution was added to adjust acidity. Crystals were extracted with hexane while extraction with EA followed by removal of solvent gave 21 g (yield 76%) of (10- (naphthalen-2-yl) anthracene-9-yl) boronic acid.

Synthesis Example 10-2) Synthesis of 3-iodonaphthalen-2-yl trifluoromethanesulfonate

Synthesis Example 10-2-a) Synthesis of 3-iodo-2-naphthol

Scheme 10-2-a)

In a round bottom flask, 100 g (628 mmol) of 3-amino-2-naphthol is dissolved in 300 mL of acetic acid, cooled to 0 ° C., and 200 mL of sulfuric acid is slowly added dropwise. After completion of the dropwise addition, 52 g (754 mmol) of sodium nitrite was added dropwise to water, stirred for 1 hour at the same temperature, and then heated to room temperature. Then, 3 g of ice and urea were added thereto, and cooled to 0 ° C. do. After the addition was completed, the mixture was stirred at room temperature, treated with sodium thiosulfate, extracted, concentrated and separated by column to obtain 3-iodo-2-naphthol. (105 g, 61.9% yield)

Synthesis Example 10-2-b) Synthesis of 3-iodonaphthalen-2-yl trifluoromethanesulfonate

Scheme 10-2-b)

19.6 g (73 mmol) of 3-iodo-2-naphthol obtained in Synthesis Example 10-2-a was added to a round bottom flask, and dissolved with dichloromethane. Then, 7 mL (87 mmol) of pyridine was added and cooled to 0 ° C.

Anhydrous 14.7 mL (87 mmol) of trifluoromethanesulphonic acid was slowly added dropwise, and when complete, the reaction mixture was warmed to room temperature and stirred sufficiently. After confirming with TLC, 2 M hydrochloric acid was added, stirred, extracted, concentrated and column separated to obtain a product. (22 g, yield 75.3%)

Synthesis Example 10-3) Synthesis of 3- (10- (naphthalen-2-yl) anthracene-9-yl) naphthalen-2-yl trifluoro methanesulfonate

Scheme 10-3)

In a round bottom flask, 22 g (55 mmol) of 3-iodonaphthalen-2-yl trifluoromethanesulfonate prepared in Synthesis Example 10-2), (10- ( Naphthalen-2-yl) anthracene-9-yl) boronic acid 20.9 g (60 mmol) tetrakis (triphenylphosphine) palladium (0) 1.27 g, (1 mmol), potassium carbonate 15.2 g (109 mmol), tetrahydro Add 110 mL of furan, 110 mL of toluene, 44 mL of water and reflux. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with ethyl acetate / water, the organic layer was concentrated and column separated to obtain a product. (27 g, yield 86%)

Synthesis Example 10-4) Synthesis of [Compound 10]

5.5 g (9 mmol) of 3- (10- (naphthalen-2-yl) anthracene-9-yl) naphthalen-2-yl trifluoromethanesulfonate prepared in Synthesis Example 10-3) in a round bottom flask, 1.1 g (9 mmol) of 2-pyrimidinylboronic acid, 0.4 g of tetrakis (triphenylphosphine) palladium (0), 3.3 g of potassium carbonate, 25 mL of ethanol, 25 mL of toluene, and 10 mL of water are refluxed. When the reaction was completed, the reaction solution was cooled to room temperature, extracted with ethyl acetate / water, the organic layer was concentrated and separated by column to synthesize [Compound 10]. (2.0 g, yield 50%)

MS (MALDI-TOF): m / z 509 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

117.7,125.6,126.1,126.2,126.6,127.7,128.1,128.2,129,130.9,132,132.7,132.8,133.1,134.2,135.2,137.2,156.1,164.2 [38C]

Synthesis Example 11. Synthesis of [Compound 11]

[Compound 11] was synthesized in the same manner as in Synthesis Example 10, except that 3-pyridinylboronic acid was used instead of 2-pyrimidinylboronic acid used in Synthesis Example 10-4). (3.1 g, yield 48%)

MS (MALDI-TOF): m / z 508 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

124,125.6,126.1,126.2,126.6,127.7,128.1,128.2,129,130.9,132,132.7,133,133.1,134,134.2,135.2,135.5,137.2,147.9,148.9 [39C]

Synthesis Example 12 Synthesis of [Compound 12]

The same method as in Synthesis Example 10-2) was used except that 3-amino-1-naphthol was used instead of 3-amino-2-naphthol used in Synthesis Example 10-2-a). [Compound 12] was synthesized in the same manner as in Synthesis Example 10, except that 6-quinoxalineboronic acid was used instead of 2-pyrimidinylboronic acid used in 4). (3.1 g, yield 55%)

MS (MALDI-TOF): m / z 559 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

125.3,125.6,126.1,126.2,126.3,127.1,127.7,127.9,128.1,128.2,128.3,130.9,132,132.7,133.1,134.2,134.6,134.7,134.9,137,137.2,139.7,141.1,142.7,144.8 [42C]

Synthesis Example 13. Synthesis of [Compound 13]

The same method as in Synthesis Example 10-2) was used except that 6-amino-1-naphthol was used instead of 3-amino-2-naphthol used in Synthesis Example 10-2-a). [Compound 13] was synthesized in the same manner except that 8-quinolinylboronic acid was used instead of 2-pyrimidinylboronic acid used in 4). (2.6 g, yield 42%)

MS (MALDI-TOF): m / z 558 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

121.5,124.5,125.1,125.4,125.6,126.1,126.2,127.2,127.5,127.7,127.8,128.1,128.2,130.9,132,132.7,132.8,133.1,134.1,134.2,134.7,136.3,136.4,136.7,137.2,138.1, 146.5,149.9 [43C]

Synthesis Example 14 Synthesis of [Compound 14]

The same method as in Synthesis Example 10-1) was used except that (6-methylnaphthalen-2-yl) boronic acid was used instead of 2-naphthalene boronic acid used in Synthesis Example 10-1-a). Synthesis Example 10-4) was used, except that 6-amino-2-naphthol was used instead of 3-amino-2-naphthol used in Example 10-2-a). [Compound 14] was synthesized in the same manner except that (1,10-phenanthroline-5-yl) boronic acid was used instead of 2-pyrimidinylboronic acid used in. (3.2 g, yield 43%)

MS (MALDI-TOF): m / z 623 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

21.5,121.5,123.5,125.6,126.1,126.3,127,127.3,128,128.2,130.3,130.9,131.1,131.3,131.9,132.6,132.9,133.1,134.2,135.3,135.7,136.4,137,137.2,137.5,149.9,154.6 [47C]

Synthesis Example 15 Synthesis of [Compound 15]

Synthesis Example 15-1) Synthesis of 5-bromo-1,2-diphenyl-1H-benzimidazole

4-methylbenzenesulfonic acid (3.1 g, 16 mmol) was added N ¹ -benzyl-4-bromobenzene-1,2-diamine (45 g, 160 mmol), 500 mL of dichloromethane and 30 mL of trimethylorthobenzoate. It is added to the mixed solution and reacted for about 40 hours at room temperature under nitrogen. After completion of the reaction, the organic layer was concentrated under reduced pressure, washed with 40% methanol / water and sodium hydrogencarbonate / water, and dried to obtain a product (22.3 g, yield 40%).

Synthesis Example 15-2) Synthesis of (1,2-diphenyl-1H-benzo [d] imidazol-5-yl) boronic acid

5-Bromo-1,2-diphenyl-1H prepared in Synthesis Example 15-1 instead of 9-bromo-10- (naphthalen-2-yl) anthracene used in Synthesis Example 10-1-c) The product was obtained using the same method except that benzimidazole was used (6.8 g, 37% yield).

Synthesis Example 15-3) Synthesis of [Compound 15]

The same method as in Synthesis Example 10-2) was used except that 7-amino-2-naphthol was used instead of 3-amino-2-naphthol used in Synthesis Example 10-2-a). Except for using (1,2-diphenyl-1H-benzo [d] imidazol-5-yl) boronic acid prepared in Synthesis Example 15-2 instead of 2-pyrimidinylboronic acid used in 4). Synthesized [Compound 15] using the same method as in Synthesis Example 10. (2.4g, 47% yield)

MS (MALDI-TOF): m / z 699 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

114.6,115.7,122.1,122.9,125.6,126.1,126.2,127.5,127.7,128.1,128.2,129.2,129.6,130.9,131,131.1,131.6,132.7,133,133.1,134,134.2,134.8,137.2,138.2,139.4,143.2,149.4 [ 53C]

Synthesis Example 16 Synthesis of [Compound 16]

Synthesis Example 16-1. Synthesis of 2,6-dialkyl substituted 10- (naphthalen-2-yl) anthracene-9-yl boronic acid

Synthesis Example 16-1-a) Synthesis of 2,6-dialkyl Substituted Anthracene Derivative

2-methyl-2-hexanol (35 g, 300 mmol) and anthracene (18.4 g, 100 mmol) were added to 50 mL trifluoroacetic acid and refluxed under nitrogen for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with dichloromethane. The resulting solid is filtered while concentrating the organic layer under reduced pressure, and then separated by column chromatography. Recrystallization with methanol gave the product. (6 g, yield 16%) was obtained.

Synthesis Example 16-1-b) Synthesis of 2,6-dialkyl substituted 9,10-dibromoanthracene

2,6-dialkyl substituted anthracene (6 g, 16 mmol) synthesized in Synthesis Example 16-1-a was added to 100 mL dichloroethane and bromine (2.1 mL, 40 mmol) while stirring at room temperature for 4 hours. Was added drop wise. It was poured into water and sodium sulfate was added to consume residual bromine. Then it was extracted with dichloromethane and the organic layer was dried over magnesium sulfate. The resulting material was passed through an alumina column using dichloromethane eluent, then evaporated, and methanol was added to precipitate a pale yellow solid, yielding about 7.2 g of product.

Synthesis Example 16-1-c) Synthesis of 2,6-dialkyl substituted 9-bromo-10- (naphthalen-2-yl) anthracene

In a round bottom flask, 7.2 g (13 mmol) of 2,6-dialkyl substituted 9,10-dibromoanthracene prepared in Synthesis Example 16-1-b), 2.2 g (13 mmol) of 2-naphthalene boronic acid, 3.7 g (27 mmol) of potassium carbonate, 0.3 g (3 mmol) of Pd (PPh ₃ ) ₄ , 15 ml of water, 40 ml of toluene and 40 ml of tetrahydrofuran were added and refluxed.

After completion of the reaction, the layers were separated, the aqueous layer was removed, the organic layer was concentrated under reduced pressure, and recrystallized with toluene hexane to obtain a product. (5.3 g, yield 71%) was obtained.

Synthesis Example 16-1-d) Synthesis of 2,6-dialkyl substituted 10- (naphthalen-2-yl) anthracene-9-yl boronic acid

2,6-dialkyl substituted 9- as prepared in Synthesis Example 16-1-c instead of 9-bromo-10- (naphthalen-2-yl) anthracene used in Synthesis Example 10-1-c) Boronic acid was synthesized using the same method except that bromo-10- (naphthalen-2-yl) anthracene was used.

Synthesis Example 16-2) Synthesis of 2-methyl-2H-1,2,3-benzotriazole-5-boronic acid

Scheme 16-2)

In a round bottom flask 5-bromo-2-methyl-2H-1,2,3-benzotriazole (8.5 g, 40 mmol) was dissolved in 650 mL of THF. N-BuLi (30 mL) was added slowly while cooling to -78 ° C. After the addition, the mixture was stirred at −78 ° C. for about 1 hour, and trimethyl borate (5.9 g, 56 mmol) was added thereto. After stirring at −78 ° C. for 1 hour, the mixture was stirred at room temperature for about 2 hours, and 2 N HCl was added to adjust acidity. After extraction with EA, the solvent was removed, and crystals were obtained with hexane to obtain a product. (5.5 g, yield 78%)

Synthesis Example 16-3) Synthesis of [Compound 16]

The same method as in Synthesis Example 10-2) was used except that 7-amino-1-naphthol was used instead of 3-amino-2-naphthol used in Synthesis Example 10-2-a). (2,6-bis (2-methylhexane-2-yl)-produced in Synthesis Example 16-1 instead of (10- (naphthalen-2-yl) anthracene-9-yl) boronic acid used in 3) 2-methyl prepared in Synthesis Example 16-2 using 10- (naphthalen-2-yl) anthracene-9-yl) boronic acid and replacing 2-pyrimidinylboronic acid used in Synthesis Example 10-4) above [Compound 16] was synthesized in the same manner as in Synthesis Example 10 except for using -2H-1,2,3-benzotriazole-5-boronic acid. (3.2 g, yield 47%)

MS (MALDI-TOF): m / z 758 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

14.1,23.3,26.4,29.1,38,43.9,44.4,120.1,122.3,124.7,125.1,125.4,126.1,126.2,127.2,127.4,127.7,127.9,128.1,128.2,128.8,130.1,131,131.6,132.7,133.1, 133.6,134.1,134.2,136.5,136.6,136.7,138.1,144.3,145.5,147.3 [55C]

Synthesis Example 17 Synthesis of [Compound 17]

The same method as in Synthesis Example 10-2) was used except that 2-amino-1-naphthol was used instead of 3-amino-2-naphthol used in Synthesis Example 10-2-a). [Compound 17] was synthesized in the same manner except that (1H-1,2,4-triazol-1-yl) boronic acid was used instead of 2-pyrimidinylboronic acid used in 4). (2.6 g, yield 41%)

MS (MALDI-TOF): m / z 498 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

123.4,125.1,125.6,126.1,126.2,126.3,126.7,127.7,128.1,128.2,128.3,128.8,129,130.9,132.6,132.7,133.1,134.2,137.2,138.6,138.7,143.3,153.6 [36C]

Synthesis Example 18 Synthesis of [Compound 18]

The same method as in Synthesis Example 10-2) was used except that 6-amino-1,2-naphthalenediol was used instead of 3-amino-2-naphthol in Synthesis Example 10-2-a). Except for using (1,3,4-oxadiazol-2-yl) boronic acid instead of 2-pyrimidinylboronic acid in Example 10-4) using the same method as in Synthesis Example 10 [Compound 18 ] Was synthesized. (2.6 g, yield 46%)

MS (MALDI-TOF): m / z 567 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

125.1,125.2,125.6,126.1,126.2,127.7,128.1,128.2,128.8,130.9,132.1,132.4,132.7,132.8,133.1,134.1,134.2,134.5,134.7,137.2,138.1,153.3,164.5 [38C]

Examples 1 to 18

Fabrication of Organic Light Emitting Diode

The light emitting area of the ITO glass was patterned to have a size of 2 mm × 2 mm and then washed. After mounting the substrate in the vacuum chamber, the base pressure is 1 × 10 ^-7 torr and the organic material is placed on the ITO DNTPD (700 kPa), NPD (300 kPa), [Formula 4] (95 wt%) + 5] (5 wt%) (250 mW), [Formula 1] to [Compound 18] prepared according to the present invention, and film formation were carried out sequentially (300 mV), followed by LiF (10 mV), Al (1,000 mV). Was formed in the order of), and measured at 0.4 mA.

The structures of [Formula 4] and [Formula 5] and [Compound 1] to [Compound 18] are as follows.

[Formula 4] [Formula 5]

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15]

[Compound 16] [Compound 17] [Compound 18]

Example 19

In the same manner as in Example 5, except that Liq (Lithium 8-hydroxy quinolate) corresponding to [Compound 5] prepared by the present invention in the electron transport layer and a conventionally used electron transport layer material in a weight% ratio of 50: 50 mixtures were used.

[Liq]

Example 20

Prepared in the same manner as in Example 5, except that [Formula 6] was used instead of [Formula 5] used in the light emitting layer.

[Formula 6]

Example 21

Prepared in the same manner as in Example 5, except that [Formula 7] was used instead of [Formula 5] used in the light emitting layer.

[Formula 7]

Comparative example

The organic light emitting device for the comparative example was manufactured in the same manner except for using Alq ₃ instead of the anthracene compound prepared by the present invention in the electron transport layer in the device structure of Examples 1 to 21.

[Alq ₃ ]

As shown in Table 1, the organic light emitting device including the anthracene derivative compound according to the present invention in the electron transport layer has a low voltage due to improved electron transport capability compared to the organic light emitting device employing Alq ₃ which is used as a material for the electron transport layer. It can be driven and has excellent luminous efficiency, so it can be utilized in organic light emitting devices.

10: substrate 20: anode
30: hole injection layer 40: hole transport layer
50: organic light emitting layer 60: electron transport layer
70: electron injection layer 80: cathode

Claims (14)

A first electrode;
A second electrode opposed to the first electrode; And
An organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes an electron transport layer and a light emitting layer,
The electron transport layer may be used by mixing one or more of the anthracene derivatives represented by the following [Formula A] or [Formula B] and the compound represented by the following Formula C, the mixing ratio of 10:90 to 90:10 An organic light emitting device characterized in that the range.
[Formula A] [Formula B]

In [Formula A] and [Formula B],
Y is the same or different and independently from each other hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 1 to Any one selected from 30 silyl groups;
Z is the same or different and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted silyl having 1 to 30 carbon atoms Any one selected from the group;
m and m 'are integers from 1 to 8;
When substituents Y and Z are not bonded to carbon of the aromatic ring of the naphthyl group or anthracenyl group, hydrogen is bonded;
X ₁ to X ₇ are the same as or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N, or S as a hetero atom, a cyano group, a nitro group, or a halogen group, which is adjacent to each other Can form a condensed ring of groups with aliphatic, aromatic, or aliphatic hetero;
One or two of X ₁ to X ₇ is a heteroaryl group having 2 to 20 carbon atoms that includes a nitrogen atom but does not include a pyridine group;
[Formula C]

In [Formula C],
M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, the OA is a monovalent ligand capable of single bond or coordination with the M,
O is oxygen,
A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted hetero atom O , Heteroaryl group having 2 to 50 carbon atoms with N or S Any one selected from,
When M is one metal selected from alkali metals, m = 1, n = 0,
When M is one metal selected from alkaline earth metals, m = 1, n = 1, or m = 2, n = 0,
When M is boron or aluminum, any one of m = 1 to 3, and n is any one of 0-2 to satisfy m + n = 3;
Y is the same as or different from each other, and independently of each other is any one selected from [formula C1] to [formula C39].
[Structure C1] [Structure C2] [Structure C3]

[Structure C4] [Structure C5] [Structure C6]

[Structure C7] [Structure C8] [Structure C9] [Structure C10]

[Formula C11] [Formula C12] [Formula C13]

[Formula C14] [Formula C15] [Formula C16]

[Structure C17] [Structure C18] [Structure C19] [Structure C20]

[Structure C21] [Structure C22] [Structure C23]

[Structure C24] [Structure C25] [Structure C26]

[Structure C2 7] [Structure C28] [Structure C29] [Structure C30]

[Structure C31] [Structure C32] [Structure C33]

[Structure C34] [Structure C35] [Structure C36]

[Structure C37] [Structure C38] [Structure C39]

In [Formula C1] to [Formula C39],
R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms And a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spirogory or fused ring,
The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, aryl group of 6 to 24 carbon atoms, One or more substituents selected from the group consisting of 6 to 24 arylalkyl groups, heteroaryl groups of 2 to 24 carbon atoms, heteroarylalkyl groups of 2 to 24 carbon atoms, alkylsilyl groups of 1 to 24 carbon atoms, arylsilyl groups of 1 to 24 carbon atoms It means to be replaced by. delete The method of claim 1,
Y and Z in [Formula A] and [Formula B] are the same or different, and are each independently hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 5 to 20 carbon atoms; And m and m 'are integers of 1 to 4, respectively. delete delete The method of claim 1,
At least one of the substituents X ₁ to X ₇ of [Formula A] and [Formula B] is any one of the following substituents 101 to 113, Formula 202, Formula 203, Formula 205, Formula 206, and Formula 301 to 606. An organic light emitting device characterized in that.
[Substitution 101] [Substitution 102] [Substitution 103]

[Substitution 104] [Substitution 105] [Substitution 106]

[Substituent 107] [Substituent 108] [Substituent 109]

[Substitution 110] [Substitution 111] [Substitution 112] [Substitution 113]

[Substituent 202] [Substituent 203]

[Substituent 205] [Substituent 206]

[Substituent 301] [Substituent 302] [Substituent 303]

[Substituent 304] [substituent 305] [substituent 306]

[Substituent 307] [Substituent 308]

[Substituent 401] [Substituent 402] [Substituent 403]

[Substituent 404] [Substituent 405] [Substituent 406]

[Substituent 407] [Substituent 408] [Substituent 409]

[Substituent 410] [Substituent 411] [Substituent 412] [Substituent 413]

[Substituent 501] [Substituent 502] [Substituent 503]

[Substituent 601] [Substituent 602] [Substituent 603]

[Substituent 604] [Substituent 605] [Substituent 606]

Wherein R is the same or different and independently from each other, hydrogen, deuterium, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, Substituted or unsubstituted aryl group having 6 to 60 carbon atoms, Substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, Substituted or unsubstituted alkyl silyl group having 1 to 40 carbon atoms, Substituted or unsubstituted carbon atoms 6 to 30 It may be selected from the arylsilyl group of, each substituent may be fused with a group adjacent to each other to form a ring,
n is an integer from 0 to 9,
When the substituent R is not bonded to the carbon of the aromatic ring in the heteroaryl group of the substituents 101 to 606, hydrogen is bonded.
One of R is a single bond bonded to the naphthyl groups of [Formula A] and [Formula B]. The method of claim 6,
Only one of the substituents X ₁ to X ₇ of the formula [A] and [Formula B] is an organic light emitting device, characterized in that any one of the substituents selected from the substituents 101 to 606. delete The method of claim 1,
And the organic layer further comprises at least one of a hole injection layer, a hole transport layer, a hole injection function, and a hole injection function. delete The method of claim 1,
The light emitting layer is an organic light emitting device, characterized in that consisting of a host and a dopant. delete delete delete

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